JP2002039994A - Method and device for continuously analyzing sample - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and device for continuously analyzing samples, which require only one report and a short processing time and is capable of reducing the risk of contamination of samples on the method and device for continuously analyzing samples. SOLUTION: A liquid is sucked from a container for accumulating a liquid sample. By changing the measurement conditions in an elemental analysis device with the liquid sucked, processing to obtain measurement data on the same sample under at least two types of analysis conditions is performed once or a plurality number of times.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a continuous sample analysis method and a continuous sample analyzer, and more particularly, to a continuous sample analysis method by automatically switching analysis conditions and a continuous sample analyzer using the same.

[0002]

2. Description of the Related Art Conventionally, a high-frequency inductively coupled plasma mass spectrometer has been used as an apparatus for measuring an element contained in a sample. FIG. 2 is a configuration diagram of the high frequency inductively coupled plasma mass spectrometer. This high-frequency inductively coupled plasma mass spectrometer uses a high-frequency inductively coupled plasma to excite a sample, guides the generated ions to a mass spectrometer through an interface consisting of a nozzle and a skimmer, and electrically detects the ions.
This is an apparatus for analyzing the element to be measured in the sample with high accuracy by accurately measuring the ion amount.

In FIG. 1, an outer chamber 1b and an outermost chamber 1c of a plasma torch 1 are supplied with argon gas from an argon gas supply source 3 via a gas controller 2. Also,
The sample in the sample container 4 is atomized by the nebulizer 4 ', and is then conveyed into the spray chamber 5 (for example, a glass spray chamber main body 5a) by argon gas.

Here, the spray chamber main body 5a is arranged in a triple pipe provided with a cooling jacket, and cooling water flows through the outermost pipe 5c of the triple pipe to cool the spray chamber main body 5a. I have. The sample thus cooled is again introduced into the inner chamber of the plasma torch 1 through the outlet of the spray chamber 5 by the argon gas.

On the other hand, a high-frequency current flows through a high-frequency power supply 10 through a high-frequency induction coil 6 wound around the plasma torch 1, and a high-frequency magnetic field (not shown) surrounds the coil 6.
Are formed. When electrons or ions are implanted in the argon gas near this high-frequency magnetic field, the high-frequency inductively coupled plasma 7 is instantaneously generated by the action of the high-frequency magnetic field.

Further, the inside of the fore-chamber main body 11 sandwiched between the nozzle 8 and the skimmer 9 is sucked by the vacuum pump 12 to, for example, 133 Pa. Further, a small disk 1 for preventing light from entering on the central axis is provided in the center chamber 13.
Ion lenses 14b and 14c are provided so as to keep a constant distance from the small disk 4a and the small disk, and the inside of the center chamber 13 is sucked by the first oil diffusion pump 15 to, for example, 133 × 10 ^-4 Pa. The inside of a rear chamber 17 containing a mass filter (for example, a quadrupole mass filter) 16 is suctioned to, for example, 133 × 10 ⁻⁵ Pa by a second oil diffusion pump 18.

The ions in the plasma 7 pass through a nozzle 8 or a skimmer 9 and are focused, for example, between a small disk 14a and ion lenses 14b and 14c (or quadrupole lenses), and then a mass filter. 16, the detection signal is guided to the secondary electron multiplier 19, detected, and the detected signal is sent to the signal processing unit 20 to be calculated and processed so that the analysis value of the element to be measured in the sample is obtained. It has become.

When measuring a sample, the analysis conditions of the apparatus are optimized so that the element to be measured can be measured with higher accuracy. The analysis conditions at this time are called tuning. For example,
It is assumed that certain elements can be measured with high accuracy when the plasma generation power is 1600 W, and other elements can be measured with high accuracy when the plasma generation power is 600 W.

Here, the condition of 1600 W of plasma generation power is called hot (HOT) tuning, and the condition of 600 W is called cool (COOL) tuning. 1
If there are 20 elements that you want to measure by hot tuning and 10 elements that you want to measure by cool tuning in the sample solution in one container, measure the first 20 in hot tuning mode, and for the remaining 10 Measure in cool tuning mode.

FIG. 3 is a conceptual diagram of a continuous element analysis system. In the figure, reference numeral 21 denotes a first container in which a sample solution is stored. As the first container 21, for example, a glass container having an open upper surface is used. In the case shown in the figure, for example, 100 first containers 21 are provided.
Reference numeral 22 denotes a second container containing a cleaning liquid for cleaning the tube 23 each time the first container 21 is measured. Numeral 30 is an elemental analyzer for performing elemental analysis, for example, the above-described high frequency inductively coupled plasma mass spectrometer. A tube 23 is placed in a first container 21, a sample liquid is sucked, and guided to the elemental analyzer 30;
The elements in the sample liquid are analyzed by the element analyzer 30.

The analysis operation of such a system will be described. First, the tube 23 is placed in the first container 21, the sample liquid is sucked by a pump (not shown), and supplied to the element analyzer 30. It is assumed that the element analyzer 30 is in a hot tuning mode. Elemental analysis device 3
0 detects an element measured in the hot tuning mode from the input sample liquid.

Next, the tube 23 is placed in the cleaning liquid in the second container 22 and washed. When cleaning is completed,
The tube 23 is put into the second container of the container 21 to aspirate the sample liquid, and then the element analysis device 30 performs element detection processing. Such an operation is repeated by the number of necessary containers 21. When the analysis of the sample liquid in the first container 21 is completed in the hot tuning mode, the analysis result is output using, for example, a printer.

Next, the element analyzer 30 is set to the cool tuning mode, and the sample liquid is sucked from the first container 21 and guided to the element analyzer 30 to analyze the sample liquid in the cool tuning mode. . In this case, the inside of the tube 23 is washed by putting the tube 23 into the washing solution of the second container 22. The washed tube 23 sucks the second sample liquid and guides it to the elemental analyzer 30 to analyze the sample liquid in the cool tuning mode. In this way, a predetermined number of sample liquids in the first container 21 are analyzed in the cool tuning mode, and the analysis result is output using, for example, a printer.

The reason why the sample liquid in the same container is measured in two modes is that the types of elements that can be measured in each measurement mode are different. For example, when trying to measure 30 elements, 20 are measured in the hot tuning mode and the remaining 10 are measured in the cool tuning mode.

[0015]

The conventional system has the following problems. In the case of the conventional apparatus, since a report for detecting 20 elements and a report for detecting 10 elements are obtained, it is necessary for the operator to manually re-create one report for each sample, which is troublesome. There was a problem.

In the conventional method, in each of the measurement in the mode for 20 pieces (hot tuning mode) and the mode for 10 pieces (cool tuning mode), it is necessary to use the cleaning liquid each time. If it takes about 2 minutes to analyze 100 containers 21 on the order, there is a problem that a considerable processing time is required.

When the measurement of one sample is completed and the next sample is taken, the tube 23 is washed, but is not completely washed yet, and contaminates the next sample. By reducing the number of movements of the tube 23, the chance of contamination is also reduced.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a continuous sample analysis method and a continuous sample analyzer in which only one report is required for each sample and the processing time can be shortened. The purpose is.

[0019]

According to the first aspect of the present invention, a liquid is sucked from a container for storing a liquid sample, and while the liquid is being sucked, the measurement conditions in the elemental analyzer are changed. It is characterized in that a process for obtaining measurement data under at least two kinds of analysis conditions is performed once or plural times for the same sample.

With this configuration, elemental analysis can be performed in a plurality of measurement modes, so that only one report is required in a plurality of modes and only one cleaning liquid is used, so that processing time is reduced. Can be hidden,
In addition, the risk of contamination of the sample can be reduced.

(2) The invention according to claim 2 is characterized in that a high frequency inductively coupled plasma mass spectrometer is used as the elemental analyzer. With such a configuration, element analysis can be performed with high accuracy using a high-frequency inductively coupled plasma mass spectrometer as an elemental analyzer.

(3) The invention according to claim 3 provides a means for sucking a liquid from a container for storing a liquid sample and at least two types of the same sample by changing measurement conditions in an elemental analyzer while the liquid sample is being sucked. Means for performing a process of obtaining measurement data under the above analysis conditions once or a plurality of times.

With this configuration, the elemental analysis can be performed in a plurality of measurement modes, so that only one report in a plurality of modes is required, and the use of a cleaning liquid is required only once, thereby shortening the processing time. Can be hidden,
In addition, the risk of contamination of the sample can be reduced.

[0024]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a flowchart showing an embodiment of the operation of the present invention. The system shown in FIG. 3 is used as a continuous elemental analysis system. First, the element analyzer 30 is set to a first mode (for example, a hot tuning mode) (S1). Next, container 2
1 and aspirates the sample liquid to give to the elemental analyzer 30 (S
2). The suction is performed by a motor (not shown).

In the element analyzer 30, the sample liquid is jetted into the plasma to be ionized, and the ionized element is analyzed (S3). By this elemental analysis, for example, the qualitative and quantitative determination of the above-mentioned 20 elements can be performed.

Next, the element analyzer 30 is set to a second mode (for example, a cool tuning mode) while the suction state of the sample liquid by the tube 23 is maintained (S4). Next, the sample solution sucked from the container 21 is applied to the elemental analyzer 3.
0 (S5). In the element analyzer 30, the sample liquid is injected into the plasma to be ionized, and the ionized element is analyzed (S6). By this elemental analysis, for example, the qualitative and quantitative determination of the ten elements as described above can be performed, and a report is output by combining the data measured in the first mode and the data measured in the second mode (S
7).

Next, it is checked whether the element analysis has been completed for all the containers (S8). If the elemental analysis has not been completed for all the containers, the suction from the container 21 is stopped, and the tube 23 is placed in the cleaning liquid of the container 22 to perform cleaning (S9). Thereafter, the flow returns to step S1 to return to the next container 2
The sample is sucked from 1 and the elemental analysis of the sample liquid is performed. When such elemental analysis processing is repeated a predetermined number of times, for example, 1
Elemental analysis can be performed on the 00 containers 21. When the elemental analysis has been completed for all the containers 21, the operation of the entire apparatus ends.

As described above, according to the present embodiment, at least two kinds of modes are measured in a state in which the sample liquid is sucked from the container 21, so that the element analysis can be performed without cleaning the tube 23. Since it can be performed, the processing time is short. When the process is completed, the results of elemental analysis in at least two modes are output as one report, so that the time required for the operator to manually create one report as in the past has been obtained. It becomes unnecessary. Also, the risk of the sample being contaminated with the previous sample is reduced.

Here, the elemental analyzer 30 includes:
Devices based on various measurement principles can be used,
The use of a high-frequency inductively coupled plasma mass spectrometer enables elemental analysis with high accuracy.

Further, in the embodiment, the description has been made using the hot tuning mode for switching the plasma generation power and the cool tuning mode as the two types of modes.
The parameter is not limited to the plasma generation power, and any parameter that can be changed, such as an ion lens voltage, an argon gas flow rate, and a plasma-nozzle distance, may be used. One parameter may be changed, or a plurality of parameters may be changed simultaneously.

In the above embodiment, the case where an elemental analyzer capable of switching between two types of modes is used as an example, but the present invention is not limited to this.
Switching of three or more types of modes may be performed. In that case, one report is created for a plurality of modes. If the report does not fit on one sheet, the report may be plural.

In the above-described embodiment, the case where the samples in all the containers are analyzed is taken as an example. However, the present invention is not limited to this, and the present invention is not limited thereto. The present invention can be applied to a case where only a sample is analyzed.

[0033]

EXAMPLE As a result of analyzing nitric acid used in semiconductor manufacturing using the present invention, B and Zn were determined by hot tuning, and Na, Mg, Al, K, Ca and C were determined by cooling tuning.
r, Mn, Fe, Ni, Cu, and Pb were detected, and could be printed as one report.

[0034]

As described above, according to the present invention, the following effects can be obtained.

(1) According to the first aspect of the present invention, since elemental analysis can be performed in a plurality of measurement modes, only one report is required in a plurality of modes and only one cleaning liquid is used. Therefore, the processing time can be shortened. Also, the risk of contamination of the sample can be reduced.

(2) According to the second aspect of the present invention, element analysis can be accurately performed by using a high-frequency inductively coupled plasma mass spectrometer as an elemental analyzer. (3) According to the third aspect of the present invention, since elemental analysis can be performed in a plurality of measurement modes, only one report is required in a plurality of modes, and only one cleaning liquid is used. Can shorten the time,
In addition, the risk of contamination of the sample can be reduced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an embodiment of the operation of the present invention.

FIG. 2 is a configuration diagram of a high-frequency inductively coupled plasma mass spectrometer.

FIG. 3 is a conceptual diagram of a continuous element analysis system.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 21 1st container 22 2nd container 23 tube 30 Elemental analyzer

Continued on the front page (72) Inventor Sayuri Miyata 1-15-1-5 Nakamachi, Musashino City, Tokyo Mitaka Takagi Building Yokogawa Analytical Systems Co., Ltd. (72) Inventor Junichi Takahashi 1-15-5 Nakamachi, Musashino City, Tokyo No. Mitaka Takagi Building Yokogawa Analytical Systems Co., Ltd. (72) Inventor Kazuo Yamanaka 1-15-5 Nakamachi, Musashino-shi, Tokyo Mitaka Takagi Building Yokogawa Analytical Systems Co., Ltd. F-term (reference) 2G058 AA01 AA05 EA03 EA14 FB05 GA20 5C038 GG09 GH13 GH15 HH02 HH28

Claims (3)

[Claims] 1. A process for aspirating a liquid from a container for storing a liquid sample, changing a measurement condition in an elemental analyzer while the suction is being performed, and obtaining measurement data under at least two types of analysis conditions for the same sample. A continuous analysis method for a sample, wherein the method is performed one or more times. 2. The continuous sample analysis method according to claim 1, wherein a high frequency inductively coupled plasma mass spectrometer is used as the elemental analyzer. 3. A means for aspirating a liquid from a container for storing a liquid sample, and changing measurement conditions in the elemental analyzer while aspirating the liquid sample to obtain measurement data of the same sample under at least two types of analysis conditions. A continuous sample analyzer comprising: means for performing the analysis one or more times.