JPH06324026A - Liquid chromatrography device - Google Patents

Abstract

PURPOSE:To achieve a complete mixing of a liquid solution even at a low flow-rate state by constituting a mixing chamber where a solvent medium from a pump is supplied to one edge and the solvent medium is supplied from the other edge to a channel switching means and a mixing means with a porous medium stored inside and then eliminating the clearance between both chambers. CONSTITUTION:A mixer 23 is provided with a cylindrical stainless container 232 and a cylindrical mixing chamber 232a corresponding to the outer shape is formed at the container 232. A cylindrical porous resin 234 corresponding to the inner diameter and the length is filled into the mixing chamber 232a. The resin 234 consists of, for example porous teflon resin, and is formed by punching a resin plate with a specific diameter. The resin disks thus punched are laminated and filled to a specific thickness within the mixing chamber 232a, thus preventing a clearance for forming a dead space from virtually existing inside the mixing chamber 232a and hence completely mixing a solvent medium when executing liquid chromatography.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to liquid chromatography, and more particularly to a liquid chromatography device using a semi-micro column.

Liquid chromatography devices are widely used as chemical analysis means for separating and quantifying chemical substances. In particular, a liquid chromatography apparatus using a semi-micro column having an inner diameter of 1 to 2 mm has an advantage that it can provide highly sensitive, high resolution and highly accurate analysis results, and active research has been made.

By the way, in liquid chromatography, a gradient method in which the composition of a solvent flowing through a column is changed with time is generally used. In the gradient method, it is necessary to accurately control the composition of the solvent, and for this purpose, a mixer for mixing a plurality of solvents supplied from a plurality of pumps is used.

When a semi-micro column having a small inner diameter is used in the gradient method, it is necessary to set the flow velocity of the fluid constituting the mobile phase flowing through the column to a value as low as about 1/5 to 1/10 of that of an ordinary column. There are various problems that need to be solved in relation to.

[0005]

2. Description of the Related Art FIG. 6 is a block diagram showing a schematic configuration of a conventional liquid chromatography apparatus compatible with the gradient method.

Referring to FIG. 6, the liquid chromatography apparatus includes a first pump 11A for feeding a first solvent A,
A second pump 11B for feeding the second solvent B,
The pumps 11A and 11B are controlled by the system controller 12 to supply the developing solvents A and B to the mixer 13.
The solvents A and B are mixed at a desired mixing ratio in the mixer 13, and then the sample solution held in the syringe 15 is injected in the sampler 14, and the sample solution is supplied to the column 16 together with the solvents A and / or B. When passing through the column 16, the chemical substances in the sample solution are separated and supplied to the detector 17 together with the solvent. The detector 17 quantitatively and / or qualitatively analyzes the chemical substances contained in the supplied solvent A and / or B. After analysis in the detector 17, the solvent and chemicals are discarded as waste in the waste sump 18.

[0007]

FIGS. 7A and 7B show a mixer 13 and its characteristics which have been conventionally used in a liquid chromatography apparatus having the structure shown in FIG.

The mixer 13 shown in FIG. 7 (A) mixes the liquids A and B using a stirrer 13a which rotates at high speed in a stirring chamber 13b to which the solvents A and B are supplied. However, in the configuration of FIG. 7 (A), a dead space 13x is formed along the wall of the stirring chamber 13b, and substantially no liquid stirring occurs in this dead space 13x. In particular, in a system with a low flow rate such as a semi-micro column, the effect of the dead space 13x becomes remarkable.

FIG. 7A shows the solvent A in the apparatus of FIG.
As the solvent B, and as the solvent B, a mixture of methanol and a small amount (0.05% by volume) of acetone is used.
The case where acetone in the solvent is detected while changing the mixing ratio according to the step-shaped program curve shown on the left side of the figure is shown. In this experiment, only the solvents A and B were made to flow through the column 16, and the total flow rate at that time was set to 200 μl / min. Detection of acetone was performed by absorption at an ultraviolet wavelength of 254 nm. In FIG. 7 (A), it can be seen that when the mixing ratio of the solvent B is linearly increased and then maintained at a level of 50%, a temporary decrease of the mixing ratio occurs. Further, the measured curves generally have rounded shoulders, which indicates that the actual control of the mixing ratio of the solvent cannot follow the desired program control.

FIG. 7B shows another mixer proposed to solve the drawbacks of the mixer 13 using the stirrer shown in FIG. 7A and its characteristics. The mixer 1 of FIG. 7 (B)
In No. 3, the beads 13c are filled in the stirring chamber 13b, and the solvents A and B are passed through the irregular passages formed between the beads to perform mixing. The configuration of FIG. 7B solves the problem of the irregular change of the mixing ratio when the program mixing ratio is suddenly changed, which has occurred in the configuration of FIG. 7A. However, in the curve of FIG. 7B, the shoulder portion is still round, and the control of the solvent mixing ratio does not sufficiently follow the program. It is considered that this is because the dead space 13x is formed in the stirring chamber 13b even in the configuration of FIG. 7 (B).

FIGS. 8A and 8B show the structure of a sampler 14 conventionally used in the apparatus shown in FIG.

Referring to FIG. 8A, the sampler 14 is composed of a hexagonal valve including a rotatable valve body 14R, and the valve body 14R has straight tubular through passages 14 _{1 to} 14 ₆ and these. Connecting flow paths 14a to 14c are formed. Here, the flow path 14a connects the flow paths 14 ₁ and 14 ₆ , the flow path 14b connects the flow paths 14 ₂ and 14 ₃ , and the flow path 1
4c connects the flow paths 14 ₅ and 14 ₆ . In the state of FIG. 8A, each of the flow paths 14 _{1 to} 14 ₆ has a port P connected to the mixer 13 and a port A ₁ connected to one end of a sample storage loop 14 ₇ described below. , A port S connected to the syringe 15, a port D connected to the waste reservoir 18, a port A ₂ connected to the other end of the loop 14 ₇ and a port C connected to the column 16, resulting in a mixer. Solvents A and B supplied from 13 are supplied to the column 16 through the channels 14 ₁ , 14 a and 14 ₆ . That is, in this state, only the solvent is supplied to the column, and the sample is not supplied. On the other hand, the syringe 15 in this state communicates with the loop 14 ₇ through the flow path 14 _3, 14b and 14 _2, further loop 14 ₇ flow path 14 _5, 14c and 14 ₄ through a communicating with the waste reservoir 18. Therefore, in the state of FIG.
By injecting the sample solution from No. 5, the sample solution is held in the loop 14 ₇ .

In FIG. 8B, the valve body 14R is rotated in the direction of the arrow, and as a result, the port P is connected to the flow paths 14 ₂ and 14b.
And 14 ₃ to loop 14 ₇ and port C to channels 14 ₁ , 14a and 14 ₆ . As a result, the solvent supplied from the mixer 13 conveys the sample solution held in the loop 14 ₇ to the column 16 via the port C. As a result, the sample solution is injected into the column 16. In addition, the syringe 15 is the flow path 1
It is connected to the waste liquid reservoir 18 via 4 ₄ , 14 c and 14 ₅ .

FIG. 9 shows the hexagonal valve 1 shown in FIGS. 8 (A) and 8 (B).
4 shows a specific configuration of No. 4.

Referring to FIG. 6, the hexagonal valve 14 includes a cap 14S which constitutes a stationary member, a valve body 14R which is rotatably attached to the cap 14S, and a passage 14a which is integrally attached to the valve body 14R. , 14b and 14c are carried by the second valve body 14R _2, and straight valve channels 14 _{1 to} 14 ₆ are formed in the valve body 14R.
In addition, the ports P, A ₁ , corresponding to the flow path in the valve body 14R,
S, D, A ₂ and C are sequentially formed. By rotating the valve body 14R with respect to the stationary cap 14S, the switching of the flow paths described in FIGS. 8A and 8B is achieved.

By the way, in the six-way valve 14 having the structure shown in FIG. 9, the flow paths 14 _{1 to} 14 in the valve body 14R are arranged.
₆ and the corresponding flow passage 14 in the valve body 14R _2.
In order to avoid the risk that the a, 14b, and 14c do not match due to an error in processing accuracy, the flow paths 14a to 14a are generally used.
c is formed with a margin. As a result, dead spaces are formed also in the flow paths 14a to 14c as indicated by the reference numeral 14ax in FIG. 10, and as a result, for example, as shown in FIG.
_When sent to ₇ , the sample solution may partly remain in the dead space of the channel 14a. If the supply of the sample solution to the column 16 is thus incomplete, an error will occur in the measurement performed by the detector 17.

Therefore, the present invention has been made in view of the above problems.
A general purpose is to provide a new and useful liquid chromatography device.

A more specific object of the present invention is to provide a liquid chromatography apparatus for performing liquid chromatography by a gradient method, the apparatus including a mixer capable of substantially completely mixing a solvent even in a low flow rate state. To do.

Another object of the present invention is to provide a liquid chromatography apparatus equipped with a sampler configured so that the sample solution can be completely supplied to the column without leaving.

[0020]

The present invention has the above-mentioned problems.
A plurality of pumps 11A, 11B for feeding a plurality of solvents
And; mixing a plurality of solvents fed from the plurality of pumps
Mixing means 23 for controlling the plurality of pumps,
The control for controlling the mixing ratio of the solvents mixed by the mixing means.
Control means 12; supplied with the solvent from the mixing means,
Chromatograph for separating a sample transported in the solvent
A column 16; the mixing means and the chromatographic color
And the solvent is supplied from the mixing means.
Further, the sample is supplied, and the sample is mixed with the solvent.
Flow path control means 2 for supplying to the chromatographic column
4; supplied with the sample separated from the column,
Liquid chromatograph comprising detection means 17 for detecting
In the device: the mixing means 23 is fed from the pump.
First end 23 supplied with solvent to be delivered _{1 a}, 23_1b，
23₁And supplying the solvent to the flow path switching means 14.
Second end 23₆And between the first end and the second end
Mixing chamber 23 extending and having a predetermined inner surface size and shape
₂, 23_2aAnd the inside dimensions stored in the mixing chamber
Pores with external dimensions and shapes corresponding to the shape and shape
Quality medium 23_FourAnd the outer dimensions of the porous medium.
The method and shape depend on the inner surface of the mixing chamber and the porous medium.
Set so that no substantial gap is formed between the outer surface and
Liquid chromatography equipment characterized by
Or a plurality of pumps 11 for feeding a plurality of solvents
A, 11B and a plurality of pumps fed from the pumps
Mixing means 23 for mixing solvents; controlling the plurality of pumps
Controlling the mixing ratio of the solvent mixed by the mixing means.
Control means 12 for controlling; and the solvent from the mixing means
Chromatograph that separates the sample that is supplied and transported through the solvent.
A mattograph column 16; the mixing means and the chromatograph
Arranged between the graph column and supplied from the mixing means
First supplying a solvent to the chromatographic column
And the sample is injected into the channel means 24a of
A second supply to the chromatographic column with a solvent
Channel means 24b, 24₇And select the second flow path means
And third flow path means 24c for communicating with the waste liquid reservoir
A flow path switching means 24 composed of a hexagonal valve;
The separated sample is supplied from the column and detected.
In the liquid chromatography device comprising the detection means 17
In addition to the six-way valve, the flow path switching means 24 is
Sample holding section 14 for injecting the sample and holding it₇Including
Only; said six-way valve: each connected to said mixing means 23
The first port P and the sample holder 14₇First end of
Second port A connected to₁And the sample is injected
3 port S and 4th port D connected to the waste liquid reservoir
And the sample holder 14₇Connected to the second end of the
Port A of 5₂Connected to the chromatographic column 16.
A stationary member 24S having a sixth port C formed therein;
Slidable on the first surface 24f with respect to the stationary member
And is pivotally movable between the first state and the second state.
And the first to sixth flow paths 24 are formed.₁~ 24₆The first
In the state of₁Matches port P above
The second flow path 24₂Is the port A₁Matches
The third flow path 24₃Matches the port S, the
4 channels 24_FourCoincides with the port D, and the fifth flow
Road 24_FiveIs the port A₂Corresponding to the sixth channel
24₆Match the port C, and the second
In the state of₁Matches port C above
The second flow path 24₂Matches the port P and
Note third flow path 24₃Is the port A₁Matches the above
4 channels 24_FourCoincides with the port S and the fifth stream
Road 24_FiveCorresponds to the port D, and the sixth flow path 24
₆Is the port A₂The rotation itself formed to match
An existing valve body 24R; on the valve body 24R,
On the second surface 24g facing the first surface 24f,
First flow path 24₁And the sixth channel 24₆First connecting with
Of the passage 24a, the second flow path and the third flow path
The second passage 24b for connection, the fourth flow path and the
And the third passage 24c connecting to the flow path of
Is formed as a groove on the surface of the
A seal member 24 that rotates integrally with the valve body is provided on the surface.
R ₂Is formed in close contact with the second surface
Achieved by a liquid chromatography device characterized by
To do.

[0021]

According to the first feature of the present invention, the solvent is mixed in the porous medium, and in that case, a dead space is not substantially formed in the mixing chamber constituting the mixing means. Therefore, substantially all the solvent supplied to the mixing chamber is mixed when passing through the porous medium.

According to the second feature of the present invention, since the groove serving as a passage for the solvent is formed on the bottom surface of the valve body of the hexagonal valve, a large passage is formed in the seal member in consideration of processing accuracy as in the conventional case. There is no need to form, so that no dead space is formed in the solvent passage in the hexagonal valve.
As a result, by passing the solvent through the hexagonal valve, the sample held in the sample holding section can be sent to the column substantially completely, and highly accurate analysis can be performed.

[0023]

1 is a sectional view showing the structure of a mixer 23 according to a first embodiment of the present invention used in the liquid chromatography apparatus of FIG.

[0024] Referring to FIG. 1, mixer 23 consists of a stainless steel container 23 ₂ having a cylindrical outer shape, the container 23
₂ has a cylindrical mixing chamber 23 _2a corresponding to its outer shape. The mixing chamber 23 _2a is typically 1.0~5.0mm
With an inner diameter of 3 to 10 cm.

[0025] The mixing chamber 23 in _2a, corresponding to the inner diameter and length of the mixing chamber 23 _2a as shown in FIG. 2, 1.0 to 5.
0mm outer diameter and a porous resin 23 ₄ cylindrical length of 3~10cm is filled. For example, the mixing chamber is 1.5m
When the inner diameter is m, the outer diameter of the resin 23 ₄ is also 1.5 mm.
Is set to. Resin 23 ₄ is made of for example porous Teflon resin, it is formed by punching a plate of porous Teflon resin to a predetermined diameter. As shown in FIG. 2, the mixing chamber 23 _2a
Inside, the resin disk 2 punched out in this way
3 _4a , 23 _4b , ... _Are stacked and filled in a predetermined length. By forming the resin 23 ₄ Thus,
There is substantially no gap that forms a dead space in the mixing chamber _232a .

Referring again to FIG. 1, stainless steel sintered filters 23 ₇ and 23 ₈ are formed at both ends of the resin 23 ₄ , and stainless steel caps 2 are also provided at both ends thereof.
3 ₃ and 23 ₅ are formed. The caps 23 ₃ and 23 ₅ are provided with ends 23 ₁ and 23 ₆ , respectively, and are screwed to the container 23 ₂ . The end portion 23 ₁ is divided into two end portions 23 _1a , 2
3 _1b , and the solvents A and B are supplied from the pumps 11A and 11B, respectively. The mixed solvent A + B is supplied to the sampler 24 from the end portion 23 ₆ .

Next, a second embodiment of the present invention will be described with reference to FIG.

Referring to FIG. 3, in the present embodiment, another six-way valve 24 is used as a sampler instead of the six-way valve 14 shown in FIG. The six-way valve 24 of FIG. 3 is a stationary cap 24 having substantially the same structure as the stationary cap 14S shown in FIG.
The valve element 24R which has S and is rotatable is engaged with this. More specifically, the valve body R includes the first plane 24f and the second plane 24f.
Has a cylindrical shape extending between the flat surface 24g of the stationary cap 24S and the corresponding flat surface (not shown) of the stationary cap 24S in the first flat surface 24f. The flat surface 24f and the flat surface of the cap 24S engaging with the flat surface 24f are in close contact with each other to form a seal.

In the valve body 24R, straight tubular channels 24 _{1 to} 24 ₆ penetrate from the plane 24f to the plane 24g as in the case of the valve body 14R, and in this embodiment, the channels 14a to 14c are provided on the plane 24g. Corresponding to, the flow paths 24a to 24c are formed in the shape of grooves. For example, when the valve body 24R is made of ceramics, the flow passages 24a to 24c are provided in the valve body 2
It is formed by simultaneously machining the channels 24 _{1 to} 24 ₆ in a 4R green body. In addition, the valve body 24R is PEEK
When formed of a resin such as (polyether ether ketone) resin, the flow paths 24a to 24c are formed at the same time as the molding of the valve body or by machining after the molding. Therefore, in the valve body 24R, the flow passages 24a to 24c can be accurately formed in alignment with the flow passages 24 _{1 to} 24 ₆ , so that the flow passages 24a to 24c can be formed in the straight tubular flow passage 24 ₁
It is not necessary to make the diameter larger than necessary for the diameter of ~ 24 ₆ . In other words, in the present embodiment, it is possible to avoid the inconvenience that the dead space 14ax as shown in FIG. 10 is formed in the flow path 14a and the sample solution remains in such a dead space.

Further, in this embodiment, the flow paths 24a to 24c are provided.
By being formed in the valve body 24R, a simple disc can be used as the member 24R ₂ that engages with and closes the surface 24g of the valve body 24R. The member 24R ₂ is firmly fixed to the valve body 24R by means such as a screw (not shown) to form a seal.

The piping of the six-way valve 24 according to this embodiment is shown in FIG.
The description is omitted because it is the same as that described in (A) and (B). In this embodiment, the flow paths 14 _{1 to} 14 ₆ and 14 a to 14 c are respectively connected to the flow path 2 in FIGS. 8 (A) and 8 (B).
It may be replaced by 4 _{1 to} 24 ₆ and 24 a to 24 c.

FIG. 4 shows a structure for mounting the six-way valve 24 of FIG. 3 on the apparatus of FIG.

Referring to FIG. 4, valve bodies 24R and 24
R ₂ is stored in the stainless case 24C, and the stationary cap 24S is screwed to the case 24C. Further, the valve bodies 24R and 24R ₂ are integrally rotated by the rod 24D. Thread holes are formed in the cap 24S corresponding to the various ports, and corresponding pipes are screwed into the thread holes. further,
In order to inject the sample solution in the syringe 15, a guide 24i is formed on the cap 24S line.

FIG. 5 shows solvent switching response characteristics when the mixer 23 shown in FIG. 1 and the hexagonal valve 24 shown in FIG. 3 are used in the liquid chromatography apparatus shown in FIG. However, in FIG. 5, the experimental condition is that the total flow rate is 100 μl / mi.
The setting is the same as in the case of FIGS. 7A and 7B except that n is set. As can be seen from this figure, the flow rate is 100 μl / mi
It can be seen that the liquid chromatography apparatus of the present invention has a sufficient responsiveness to the change of solvent and the change of composition even when the value is made extremely small.

[0035]

As described above, according to the present invention, it is possible to remove a dead space in a stirring chamber by mixing a plurality of solvents using a porous resin that completely fills the stirring chamber. And a substantially complete mixture of solvents can be obtained when performing liquid chromatography by the gradient method. The present invention also accurately corresponds to the through-flow passage formed in the valve body by forming the connecting flow passage in the shape of a groove on the bottom surface of the cylindrical rotatable valve body in the hexagonal valve constituting the sampler. As a result, the connection channel can be formed without causing an error, and the problem of forming a dead space due to the formation of a large groove in consideration of a processing error as in the past is solved, and the sample solution Can be completely supplied to the column without being left in the sampler. As a result, in the semi-micro liquid chromatography device of the present invention, it is possible to carry out the analysis while flowing the solvent at a low flow rate, and it is possible to perform the measurement with high accuracy, high resolution and high sensitivity. Further, in the liquid chromatography device of the present invention, since the flow rate of the solvent is small, the amount of waste liquid generated is small, and the processing cost for preventing environmental pollution is low.

[Brief description of drawings]

FIG. 1 is a sectional view showing a configuration of a mixer according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a structure of a porous medium used in the mixer of FIG.

FIG. 3 is a diagram showing a configuration of a six-way valve which constitutes a sampler according to a second embodiment of the present invention.

4 is a diagram showing a configuration in which the hexagonal valve of FIG. 3 is attached to a liquid chromatography device.

FIG. 5 is a diagram showing response characteristics when the solvent composition is changed with time in the liquid chromatography device according to the present invention.

FIG. 6 is a diagram showing a configuration of a conventional liquid chromatography device.

7A and 7B are diagrams showing a configuration of a mixer used in the liquid chromatography apparatus of FIG.

8A and 8B are diagrams showing sampler piping in the liquid chromatography apparatus of FIG.

FIG. 9 is a diagram showing the configuration of a six-way valve used in a conventional sampler.

FIG. 10 is a diagram illustrating a problem of a conventional six-way valve.

[Explanation of symbols]

11A, 11B pump 12 controller 13, 23 mixers 13a stirrer 13b mixing chamber 13c beads 13x dead space 14, 24 hexagonal valve 14 _{1-14 6,} 24 _{1-24 6} straight pipe-shaped flow path 14 ₇ sample holding loop 14 a to 14 c, 24a ~24c connecting passage 14R, 14R _2, 24R, 24R ₂ valve 14S, 24S stationary cap 14ax dead space 23 _1, 23 _1a, 23 _1b, 23 ₆ pipe 23 ₂ vessel 23 _3, 23 ₅ cap 23 ₄ porous resin 23 _4a , 23 _4b Resin disk 23 ₇ , 23 ₈ Filter 24f, 24g Plane 24i Guide 24C Case 24D Rod

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yu Otsu, Yutaka Otsu, 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Inside Shiseido Research Center 1, Inc. Shiseido Research Center No. 1 (72) Inventor Michihiro Yamaguchi 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Research Center No. 1

Claims (7)

[Claims] 1. A plurality of pumps (1) for feeding a plurality of solvents.
1A, 11B); mixing means (23) for mixing a plurality of solvents fed from the plurality of pumps; controlling the plurality of pumps to adjust a mixing ratio of the solvents mixed by the mixing means. Control means (12) for controlling; a chromatographic column (16) for separating the sample supplied with the solvent from the mixing means and conveyed in the solvent; and between the mixing means and the chromatographic column A flow path control means (24) which is provided and is supplied with the solvent from the mixing means and further supplied with the sample to the chromatographic column together with the solvent; and a sample separated from the column. In a liquid chromatography device comprising a detection means (17) supplied to detect this: said mixing means (23) is supplied with the solvent delivered from said pump first End _{(23 1 a, 23 1b,} 2
3 ₁ ), a second end (23 ₆ ) for supplying the solvent to the flow path switching means (14), and a predetermined inner surface extending between the first end and the second end. A mixing chamber (23 ₂ , _{232 a} ) having a size and shape, and stored in said mixing chamber,
More becomes porous medium (23 ₄₎ having an outer dimension and shape corresponding to the inner surface dimensions and shape, the outer diameter and shape of the porous medium, the outer surface of the inner surface and the porous medium of the mixing chamber A liquid chromatography device, characterized in that it is set so that a substantial gap is not formed between the liquid chromatography device and the liquid chromatography device. 2. The chromatographic column (16) comprises one
The pump (11A, 11B) having an inner diameter of ~ 2 mm
Is the solvent, and the total flow rate is 50 μl / min to 200 μl.
The liquid chromatography device according to claim 1, wherein the liquid chromatography device is fed in the range of / min. 3. The mixing chamber (23 _2a ) has an inner diameter of 1.5.
Has a cylindrical shape of ~ 4.6 mm and a length of 3-10 cm,
The liquid chromatography device according to claim 2, wherein the porous medium (23 ₄ ) has a cylindrical shape having a corresponding outer shape and length. 4. The liquid chromatography apparatus according to claim 1, wherein the porous medium (23 ₄ ) is made of a porous resin. 5. A plurality of pumps (1) for feeding a plurality of solvents.
1A, 11B); and a compound fed from the plurality of pumps
A mixing means (23) for mixing a number of solvents;
Of the solvent mixed by the mixing means by controlling the pump.
Control means (12) for controlling the mixing ratio;
Sample supplied with the solvent and transported in the solvent.
A chromatographic column (16) for separating; said mixing hand
Disposed between the column and the chromatographic column, and
The solvent supplied from the mixing means is changed to the chromatographic color
The first flow path means (24a) for supplying the sample and the sample.
Injected, which is then injected with the solvent into the chromatograph.
Second flow path means (24b, 24) for supplying to the ram₇)When,
A second flow path means for selectively communicating the second flow path means with the waste liquid reservoir
And a six-way valve having three flow path means (24c).
Flow path switching means (24); separated from the column
And a detection means (17) for detecting the supplied sample.
In a liquid chromatography device comprising: the flow path
The switching means (24) injects the sample in addition to the hexagonal valve.
A sample holding part (14₇) Included; before
The hexagonal valve includes: a first valve connected to the mixing means (23).
1 port (P) and the sample holder (14)₇) First
The second port (A₁), And sample
Connected to the third port (S) to be inserted and the waste liquid reservoir
The fourth port (D) and the sample holder (14₇) Of
The fifth port (A₂) And chroma
Sixth port connected to the tograph column (16)
(C) a stationary member (24S) formed with;
It is slidably engaged with the member on the first surface (24f).
And is rotatably formed between the first state and the second state.
The first to sixth flow paths (24₁~ 24 ₆) Is the first
In this state, the first flow path (24₁) Is the first port
(P), and the second channel (24₂) Is the above
2 ports (A₁), The third channel (2
Four₃) Matches the third port (S) and the fourth port (S)
Channel (24_Four) Matches the fourth port (D) and
Note 5th channel (24_Five) Is the fifth port (A₂) To
And the sixth channel (24₆) Is the sixth port
(C), and in the second state,
Note First flow path (24₁) Is connected to the sixth port (C).
The second channel (24₂) Is the first port
(P), and the third channel (24₃) Is the second
Port (A₁), The fourth channel (24_Four)
Corresponds to the third port (S), and the fifth flow path
(24_Five) Matches the fourth port (D),
6 channels (24₆) Is the fifth port (A₂) Matches
With a freely rotatable valve element (24R)
On the valve body (24R), the first surface (24R)
On the second surface (24g) facing f), the first stream is
Road (24₁) And the sixth channel (24₆) Connecting with
Passage (24a), the second flow path and the third flow path
And a second passage (24b) connecting the
And a third passage (24c) connecting the fifth flow path and
Are formed as grooves on said second surface;
In addition, on the second surface, it rotates integrally with the valve body.
Seal member (24R₂) Is in close contact with the second surface
Liquid chromatograph characterized by being formed by
Fi device. 6. The valve body (24R) has a cylindrical shape,
The liquid chromatography device according to claim 5, wherein the liquid chromatography device is made of ceramics. 7. The liquid chromatography apparatus according to claim 5, wherein the valve body (24R) is made of resin.