Column protection cover and gas chromatograph
The detachable column protection cover with insulating material allows gas chromatograph apparatuses to operate at higher temperatures by protecting columns with lower maximum operating temperatures, improving operational flexibility and reducing maintenance.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- SHIMADZU CORP
- Filing Date
- 2025-11-17
- Publication Date
- 2026-06-11
Smart Images
Figure JP2025040174_11062026_PF_FP_ABST
Abstract
Description
Column protective cover and gas chromatograph apparatus 【0001】 The present invention relates to a column protective cover attached to a column for gas chromatography, and a gas chromatograph apparatus equipped therewith. The gas chromatograph apparatus referred to herein includes, of course, gas chromatograph-mass spectrometers in which the detector is a mass spectrometer, regardless of the type of detector. 【0002】 In gas chromatography systems, various sample introduction devices are used to introduce the sample gas into the column, depending on the type and characteristics of the sample. For example, when analyzing volatile compounds, a headspace sample introduction device is used, which collects a fixed amount of sample gas evaporated from a liquid sample stored in a container and sends it to the column. When analyzing other compounds, a liquid sample introduction device is generally used, which vaporizes the liquid sample in a high-temperature sample vaporization chamber and sends the resulting sample gas to the column. 【0003】 The separation characteristics of the column used for component separation must also be different for volatile compounds and other compounds. Therefore, different columns are often used when using a liquid sample introduction system compared to a headspace sample introduction system. Specifically, when using a liquid sample introduction system, nonpolar or slightly polar columns (hereinafter collectively referred to as nonpolar / slightly polar columns) with a high maximum operating temperature (the upper limit of the operating temperature specified for the column) are used to accommodate a variety of compounds. On the other hand, when using a headspace sample introduction system, medium-polar or highly polar columns (hereinafter collectively referred to as medium-polar / high-polar columns) suitable for the analysis of highly polar and volatile compounds are used. However, providing both a gas chromatograph equipped with a headspace sample introduction system and medium-polar / high-polar columns, and a gas chromatograph equipped with a liquid sample introduction system and nonpolar / slightly polar columns, represents a significant financial burden. 【0004】Therefore, conventionally, there has been a gas chromatograph apparatus that can appropriately switch between analysis using a headspace sample introduction device and a medium-polarity / high-polarity column and analysis using a liquid sample introduction device and a non-polarity / weak-polarity column (see, for example, Patent Document 1). Such a gas chromatograph apparatus includes a column oven capable of accommodating two columns in parallel. Among the two columns, the inlet end of one column is connected to the headspace sample introduction device, and the inlet end of the other column is connected to the liquid sample introduction device. Also, the outlet ends of the two columns are both connected to a detector such as a mass spectrometer via an interface. Then, when the user selects one of the above sample introduction devices according to the type of compound to be analyzed, sample gas is introduced from the selected sample introduction device to the column connected to the sample introduction device, and the sample gas component-separated by the column is detected by the detector. 【0005】 Japanese Patent Application Laid-Open No. 2006-162515 【0006】 However, in a gas chromatograph apparatus having a function of switching and using two columns as described above, since the two columns are accommodated in the same column oven, there is a restriction that the temperature of the column oven cannot be made higher than the maximum operating temperature of the column with the lower maximum operating temperature among the two columns. 【0007】 The present invention has been made in view of the above points, and an object thereof is to eliminate the above-described restrictions in a gas chromatograph apparatus provided with a column oven in which a plurality of columns are accommodated in parallel. 【0008】To solve the above problems, the column protection cover according to the present invention includes a sheet-like insulating material that covers a column of a gas chromatograph, and is a cover that can be detachably attached to the column, comprising: a winding portion accommodating region that accommodates the annularly wound portion of the column; an inlet-side unwinding portion accommodating region that accommodates the inlet-side portion of the unwinding portions at both ends of the column; an outlet-side unwinding portion accommodating the outlet-side portion of the unwinding portions at both ends of the column; a column insertion / removal port for inserting and removing the column; an opening / closing mechanism for opening and closing the column insertion / removal port; an inlet-end projection that causes the inlet end of the column to protrude outside the cover when the column insertion / removal port is sealed by the opening / closing mechanism; and an outlet-end projection that causes the outlet end of the column to protrude outside the cover when the column insertion / removal port is sealed by the opening / closing mechanism. 【0009】 Furthermore, the gas chromatograph apparatus according to the present invention, which was developed to solve the above problems, comprises a column oven in which a plurality of columns are installed in parallel, and a column protective cover including a sheet-like insulating material that covers the column and is detachably attached to some of the columns among the plurality of columns. 【0010】 According to the column protection cover and gas chromatograph apparatus of the present invention described above, when a column with a relatively low maximum operating temperature is not used among a plurality of columns installed in a column oven, the column protection cover can be attached to that column to protect it from temperature damage. Therefore, in a gas chromatograph apparatus in which a plurality of columns are housed in parallel in a column oven, the column oven can be used at a temperature higher than the maximum operating temperature of the column with the relatively low maximum operating temperature. 【0011】 A schematic diagram of a gas chromatograph apparatus according to one embodiment of the present invention. A schematic diagram of a gas chromatograph apparatus according to another embodiment of the present invention. A diagram showing another example of the shape of the column protection cover according to the present invention. A diagram showing yet another example of the shape of the column protection cover according to the present invention. 【0012】 The embodiments for carrying out the present invention will be described below with reference to the drawings. Figure 1 is a schematic diagram of a gas chromatograph apparatus according to this embodiment. This gas chromatograph apparatus includes a first sample introduction section 110, a second sample introduction section 120, a column oven 130, a detector 140, and a column protective cover 150. In the figure, the column oven 130 is shown in cross-section. Hereafter, the front and back and left and right will be defined as the front side in the direction of the paper in Figure 1 and the right side in the figure being the right side. 【0013】 The column oven 130 is equipped with a chamber 131 capable of housing two columns. Hereinafter, one of the two columns will be referred to as the first column 160 and the other as the second column 170. In Figure 1, for illustrative purposes, the second column 170 is positioned below the first column 160, but in reality, the second column 170 is positioned behind the first column 160. The front of the chamber 131 is an openable and closable door (not shown), and on the back surface of the chamber 131 opposite the door, column hangers (not shown) for mounting the first column 160 and the second column 170 are provided. Also on the back surface, a heater, a fan, and a temperature sensor (all not shown) are provided for temperature control of the internal space of the chamber 131. 【0014】The first sample introduction unit 110 is a headspace sample introduction device that collects a fixed amount of sample gas vaporized from a liquid sample stored in a container (not shown) and sends it to the column. The second sample introduction unit 120 is a liquid sample introduction device that vaporizes a liquid sample in a high-temperature sample vaporization chamber (not shown) and sends the resulting sample gas to the column. These sample introduction units 110 and 120 are located at the top of the column oven 130. In Figure 1, for illustrative purposes, the second sample introduction unit 120 is shown to the left of the first sample introduction unit 110, but in reality, the second sample introduction unit 120 is located behind the first sample introduction unit 110. The first sample introduction unit 110 is connected to the inlet end of the first column 160 via a first column connection unit 111 provided on its bottom surface. The second sample introduction unit 120 is connected to the inlet end of the second column 170 via a second column connection unit 121 provided on its bottom surface. The positional relationship between the first sample introduction section 110 and the second sample introduction section 120 and the column oven 130 is not limited to the above, and the first sample introduction section 110, the second sample introduction section 120, or both may be placed next to the column oven 130. 【0015】 A so-called medium-polarity / high-polarity column is used as the first column 160 connected to the first sample introduction section 110, and a so-called non-polarity / slightly polarity column is used as the second column 170 connected to the second sample introduction section 120. The maximum operating temperatures of these columns 160 and 170 are relatively lower for the first column 160 (for example, around 240°C) and relatively higher for the second column 170 (for example, around 320°C). A post column 190 is connected to the outlet end of the first column 160 via a connecting component 191 such as a union. Hereinafter, the end of the post column 190 connected to the first column 160 will be called the front end, and the opposite end will be called the rear end. 【0016】The detector 140 detects sample components sequentially eluted from the first column 160 or the second column 170. A mass spectrometer is preferably used as the detector 140, but it is not limited thereto. For example, a detector commonly used in gas chromatographs, such as a flame ionization detector or a thermal conductivity detector, may also be used. The detector 140 is connected to the rear end of the post column 190 and the outlet end of the second column 170 via an interface 141. In Figure 1, the detector 140 is positioned to the right of the column oven 130, but the positional relationship between the detector 140 and the column oven 130 is not limited to this. The detector 140 may be positioned to the left of the column oven 130 or above the column oven 130. 【0017】 The column protection cover 150 is attached to the first column 160 when performing analysis using the second column 170 (i.e., analysis without using the first column 160). This prevents the first column 160 from being damaged or deteriorated by heat, even if the temperature inside the column oven 130 is higher than the maximum operating temperature of the first column 160. 【0018】The column protection cover 150 has a bag-like shape formed by joining two flexible sheets together at a portion of their periphery. In Figure 1, the portion of the periphery of the two sheets that is joined together is shown with a thick line (the same applies to Figures 2 to 4 described later). The sheet has a front surface (the surface that faces outwards from the bag) made of a heat-resistant sheet material, and a back surface (the surface that faces inwards from the bag) made of a sheet-like insulating material. The heat-resistant sheet material can preferably be a fabric made of heat-resistant fibers such as aramid fibers or PBO (poly(p-phenylenebenzobisoxazole)) fibers, or a fabric made of a predetermined fiber with aluminum vapor-deposited on it, but is not limited to these. The insulating material can preferably be a fibrous insulating material such as glass wool, rock wool, or ceramic wool, but is not limited to these. The column protection cover 150 is equipped with a loop-shaped or hook-shaped engaging portion (not shown) that can be hooked onto the column hanger or other suspension member provided inside the column oven 130. 【0019】The column protection cover 150 comprises a front-view rectangular winding portion housing area 151 that houses the annularly wound portion of the first column 160 (hereinafter referred to as the winding portion 161), a front-view rectangular inlet-side unwinding portion housing area 152 that houses the inlet end portion of the unwinding portions at both ends of the first column 160 (hereinafter referred to as the inlet-side unwinding portion 162), and a front-view rectangular outlet-side unwinding portion housing area 153 that houses the outlet end portion of the unwinding portion (hereinafter referred to as the outlet-side unwinding portion 163) and the front end of the post column 190. Here, the outlet-side unwinding portion 163 of the first column 160 and the post column 190 correspond to the "outlet end portion of the unwinding portions at both ends of the column" in the present invention. The inlet-side unwound portion housing area 152 and the outlet-side unwound portion housing area 153 protrude laterally from the upper left and right side edges of the winding portion housing area 151 in a front view, so that the column protection cover 150 as a whole has a roughly T-shape in a front view. The internal spaces of the inlet-side unwound portion housing area 152 and the outlet-side unwound portion housing area 153 are in communication with the internal space of the winding portion housing area 151. The two sheets constituting the column protection cover 150 are joined to each other at their peripheral edges, except for the upper edge of the T-shape and the right edge of the outlet-side unwound portion housing area 153. The upper edge of the T-shape that is not joined serves as the column insertion / removal opening 154 for inserting and removing the first column 160. The right edge of the outlet-side unwound portion housing area 153 that is not joined serves as the outlet end projection 156 for allowing the rear end of the post-column 190 (corresponding to the "outlet end of the column" in this invention) to protrude outside the column protection cover 150. 【0020】A fastener 157 is attached to the upper edge of the T-shape for opening and closing the column inlet / outlet 154 (i.e., sealing or releasing the column inlet / outlet 154). This fastener 157 corresponds to the opening and closing mechanism in the present invention. The fastener 157 can be any type that is easy to engage and disengage, such as hook-and-loop fasteners, snaps, or hooks. However, it is desirable that the fastener 157 be made of a heat-resistant material that can withstand temperatures above the maximum operating temperature of the second column 170. Furthermore, there is an area near the left end of the upper edge of the T-shape where no fastener 157 is provided, and this area is an inlet end projection 155 that allows the inlet end of the first column 160 to protrude outside the column protective cover 150. 【0021】When attaching the column protection cover 150 to the first column 160, the door of the column oven 130 containing the first column 160 and the second column 170 is opened, and with the inlet end of the first column 160 and the rear end of the post column 190 connected to the first column connection part 111 and interface 141, respectively, the wound portion 161 of the first column 160 is removed from the column hanger and inserted into the wound portion housing area 151 of the column protection cover 150 through the column inlet / outlet opening 154. Then, the inlet-side unwound portion 162 of the first column 160 is housed in the inlet-side unwound portion housing area 152, and the outlet-side unwound portion 163 of the first column 160 and the front end of the post column 190 are housed in the outlet-side unwound portion housing area 153, and the column inlet / outlet opening 154 is sealed with the fastener 157. Then, the column protection cover 150 and the first column 160 are fixed inside the column oven 130 by hooking the engaging portion provided on the column protection cover 150 onto the column hanger or other suspension member. At this time, the inlet end of the first column 160, which is inserted into the first column connection portion 111, protrudes outside the column protection cover 150 from the inlet end projection 155. Also, the rear end of the post column 190, which is connected to the outlet end of the first column 160, protrudes outside the column protection cover 150 from the outlet end projection 156. Since the post column 190 is not coated with liquid phase, as shown in Figure 1, it is not a problem even if a part of the post column 190 is exposed from the column protection cover 150. In addition, although the rear end of the post column 190 is inserted into the interface 141, for the same reasons as above, the post column 190 will not be damaged even if the interface 141 becomes hot. 【0022】 When performing analysis using the first column 160, the column protective cover 150 is removed from the first column 160 by the reverse procedure described above. 【0023】As described above, the column protection cover 150 can be attached to the first column 160 without removing the inlet and outlet ends (more precisely, the rear end of the post-column 190) of the first column 160 from the first column connection part 111 and interface 141, respectively. This reduces the burden on the operator when attaching and detaching the column protection cover 150 to the first column 160, and if the detector 140 is a mass spectrometer, the column protection cover 150 can be attached and detached without breaking the vacuum inside the mass spectrometer while the column 160 remains connected to the detector 140. 【0024】 The gas chromatograph apparatus according to the present invention may further include a mechanism for cooling the inside of the column protective cover. An example of the configuration of the gas chromatograph in this case is shown in Figure 2. In Figure 2, components that are the same as or corresponding to those shown in Figure 1 are denoted by the same last two digits and their descriptions are omitted as appropriate (the same applies to Figures 3 and 4 described later). 【0025】 In this example of a gas chromatograph apparatus, the column protection cover 250 is provided with a gas inlet 258 and a gas outlet 259, and the apparatus also includes a cooling gas supply unit 281 such as a gas cylinder located outside the column oven 230, a cooling gas supply pipe 282 that sends the cooling gas supplied from the cooling gas supply unit 281 to the gas inlet 258, a cooling gas discharge pipe 283 that discharges the cooling gas that has passed through the column protection cover 250 to the outside of the column oven 230 from the gas outlet 259, and a control unit 284 that controls the supply of cooling gas from the cooling gas supply unit 281. Here, the cooling gas supply unit 281, the cooling gas supply pipe 282, the control unit 284, and the gas inlet 258 correspond to the cooling gas inlet in the present invention, and the cooling gas outlet 259 and the cooling gas discharge pipe 283 correspond to the cooling gas discharge in the present invention. 【0026】In this configuration example, when performing analysis using the second column 270 (i.e., analysis without using the first column 260), the column protection cover 250 is attached to the first column 260 by the same procedure as described above, and the cooling gas supply pipe 282 and the cooling gas discharge pipe 283 are connected to the gas inlet 258 and gas outlet 259 of the column protection cover 250, respectively. Subsequently, heating of the column oven 230 by the heater described above is started, and when the temperature inside the column oven 230 reaches a predetermined temperature, the supply of cooling gas from the cooling gas supply unit 281 is started under the control of the control unit 284. As a result, the inside of the column protection cover 250 is cooled by the cooling gas, which more effectively prevents the first column 260 from being damaged by heat. 【0027】 Any gas may be used as the cooling gas, such as nitrogen gas or carbon dioxide gas. Furthermore, instead of the configuration with a gas cylinder as described above, the cooling gas supply unit 281 may be configured to supply air from outside the column oven 230 to the cooling gas supply pipe 282 using a fan or other blowing mechanism. In this case, the air serves as the cooling gas. 【0028】 Although specific examples of embodiments for carrying out the present invention have been described above, the present invention is not limited to the above embodiments, and modifications are permitted as appropriate in accordance with the spirit of the present invention. 【0029】 For example, the shape of the column protection cover 150 may be such that the inlet-side unwound portion housing area 152 and the outlet-side unwound portion housing area 153 protrude laterally (to the right or left) from the winding portion housing area 151, as shown in Figure 1. Alternatively, the inlet-side unwound portion housing area 152 or the outlet-side unwound portion housing area 153 or both may protrude upward from the winding portion housing area 151. As an example, Figure 3 shows a column protection cover 350 in which the inlet-side unwound portion housing area 352 protrudes upward from the winding portion housing area 351, and the outlet-side unwound portion housing area 353 protrudes laterally from the winding portion housing area 351. 【0030】Furthermore, the column protection cover 150 may be configured such that the inlet-side unwound portion housing area 152, the outlet-side unwound portion housing area 153, or both are integrated with the winding portion housing area 151. Also, in the example of Figure 1, the inlet end protrusion 155 is located on the upper edge of the inlet-side unwound portion housing area 152, and the outlet end protrusion 156 is located on the right edge of the outlet-side unwound portion housing area 153. However, the arrangement of the inlet end protrusion 155 and the outlet end protrusion 156 is not limited to this, and various arrangements can be adopted depending on the position of the first sample introduction section 110 and the detector 140 relative to the column oven 130. As an example, Figure 4 shows an example in which both the inlet-side non-winding portion housing area 452 and the outlet-side non-winding portion housing area 453 are integrally configured with the winding portion housing area 451, and the inlet end protrusion 455 and the outlet end protrusion 456 are positioned on the left side of the inlet-side non-winding portion housing area 452 and the right side of the outlet-side non-winding portion housing area 453, respectively. 【0031】 Furthermore, in the above embodiment, the column protection cover 150 is made by joining two flexible sheets at their periphery, but the column protection cover 150 may also be made of one sheet or three or more sheets. 【0032】 In either case, it is desirable that the inlet end projection 155 and the outlet end projection 156 form an opening continuous with the column inlet 154 when the column inlet 154 is open (i.e., the column inlet 154 is not sealed by the fastener 157). This makes it possible to attach and detach the column protective cover 150 to the first column 160 without removing the inlet end of the first column 160 and the rear end of the post column 190 from the first column connection part 111 and interface 141, respectively. 【0033】Furthermore, in the above example, a headspace sample introduction device was used as the first sample introduction unit 110 and a liquid sample introduction device was used as the second sample introduction unit 120. However, the present invention can be similarly applied to gas chromatographs that use other sample introduction devices used in gas chromatographs (for example, a purge / trap sample introduction device or a thermal desorption sample introduction device) as the first sample introduction unit 110 or the second sample introduction unit 120. Moreover, the present invention can be similarly applied to gas chromatographs that use the same type of sample introduction device (for example, a liquid sample introduction device) for both the first sample introduction unit 110 and the second sample introduction unit 120. 【0034】 Furthermore, in the example above, the first column 160 and the second column 170 were used as capillary columns, but the first column 160 and the second column 170 may also be packed columns. 【0035】 Furthermore, although the above example shows a gas chromatograph apparatus equipped with a column oven 130 capable of mounting two columns, a first column 160 and a second column 170, in parallel, the present invention can be similarly applied to a gas chromatograph apparatus equipped with a column oven capable of mounting three or more columns in parallel. In that case, at least the column protective cover 150 described above should be attached to the column with the lowest maximum operating temperature. 【0036】 Furthermore, in the above example, the inlet end of the first column 160 is directly inserted into the first column connection 111. However, the configuration is not limited to this. A short column without a liquid phase coating (hereinafter referred to as a pre-column) may be connected to the inlet end of the first column 160, and the front end of the pre-column (the end not connected to the first column 160) may be inserted into the first column connection 111. With this configuration, even if the first column connection 111 becomes hot, it is possible to prevent the first column 160 from deteriorating due to heat. 【0037】 [Embodiments] It will be apparent to those skilled in the art that the exemplary embodiments described above are specific examples of the following embodiments. 【0038】(Section 1) A column protective cover according to one aspect of the present invention is a cover that includes a sheet-like insulating material for covering a column of a gas chromatograph, and is detachably attached to the column, comprising: a winding portion accommodating area for accommodating an annularly wound portion of the column; an inlet-side unwinding portion accommodating the inlet-side portion of the unwinding portions at both ends of the column; an outlet-side unwinding portion accommodating the outlet-side portion of the unwinding portions at both ends of the column; a column insertion / removal opening for inserting and removing the column; an opening / closing mechanism for opening and closing the column insertion / removal opening; an inlet-end protrusion for causing the inlet end of the column to protrude outside the cover when the column insertion / removal opening is sealed by the opening / closing mechanism; and an outlet-end protrusion for causing the outlet end of the column to protrude outside the cover when the column insertion / removal opening is sealed by the opening / closing mechanism. 【0039】 (Article 2) The column protection cover relating to Article 2 is such that, in the column protection cover relating to Article 1, when the column inlet / outlet is not sealed by the opening / closing mechanism, the inlet end projection and the outlet end projection form an opening continuous with the column inlet / outlet. 【0040】 (Paragraph 3) The column protection cover relating to Paragraph 3 is a column protection cover relating to Paragraph 1 or Paragraph 2, having a cooling gas inlet for introducing cooling gas into the cover, and a cooling gas outlet for discharging the cooling gas that has passed through the cover. 【0041】 (Article 4) The gas chromatograph apparatus relating to Article 4 comprises a column oven in which a plurality of columns are installed in parallel, and a column protective cover including a sheet-like insulating material that covers the column and is detachably attached to some of the columns among the plurality of columns. 【0042】(Paragraph 5) The gas chromatograph apparatus according to Paragraph 5 further comprises, in the gas chromatograph apparatus according to Paragraph 4, a cooling gas introduction unit for introducing cooling gas into the column protective cover, and a cooling gas discharge unit for discharging the cooling gas that has passed through the column protective cover to the outside of the column oven. 【0043】 110...First sample introduction section 120...Second sample introduction section 130...Column oven 140...Detector 150...Column protective cover 151...Wound section housing area 152...Inlet side non-wound section housing area 153...Outlet side non-wound section housing area 154...Column inlet / outlet port 155...Inlet end protrusion 156...Outlet end protrusion 157...Fastener 160...First column 161...Wound section 162...Inlet side non-wound section 163...Outlet side non-wound section 170...Second column
Claims
1. A column protective cover comprising a sheet-like insulating material for covering a column of a gas chromatograph, and detachably attached to the column, the cover comprising: a winding portion housing area for housing the annularly wound portion of the column; an inlet-side unwinding portion housing area for housing the inlet-side portion of the unwinding portions at both ends of the column; an outlet-side unwinding portion housing area for housing the outlet-side portion of the unwinding portions at both ends of the column; a column insertion / removal opening for inserting and removing the column; an opening / closing mechanism for opening and closing the column insertion / removal opening; an inlet-end protrusion for allowing the inlet end of the column to protrude outside the cover when the column insertion / removal opening is sealed by the opening / closing mechanism; and an outlet-end protrusion for allowing the outlet end of the column to protrude outside the cover when the column insertion / removal opening is sealed by the opening / closing mechanism.
2. The column protective cover according to claim 1, wherein, when the column inlet / outlet is not sealed by the opening / closing mechanism, the inlet end projection and the outlet end projection form an opening continuous with the column inlet / outlet.
3. A column protection cover according to claim 1, comprising: a cooling gas inlet for introducing cooling gas into the cover; and a cooling gas outlet for discharging the cooling gas that has passed through the cover.
4. A gas chromatograph apparatus comprising: a column oven in which multiple columns are installed in parallel; and a column protective cover containing a sheet-like insulating material that covers some of the multiple columns and is detachably attached to some of the columns.
5. The gas chromatograph apparatus according to claim 4, further comprising: a cooling gas introduction unit for introducing cooling gas into the column protective cover; and a cooling gas discharge unit for discharging the cooling gas that has passed through the column protective cover to the outside of the column oven.