KR20180129485A - Sample pretreatment method, pretreated samples, analysis method and sample pretreatment apparatus - Google Patents

Abstract

The present invention relates to a sample pretreatment method, an analysis method using the same, and a pretreatment apparatus and, more specifically, relates to a sample pretreatment method, a pretreated sample, an analysis method using the same, and a pretreatment apparatus, wherein the sample pretreatment method comprises the following steps of: introducing a sample into the pretreatment apparatus; and treating and dispersing the sample in the pretreatment apparatus with ultrasonic waves. The sample has W/O emulsion, a material to be deposited, or both of the emulsion and the material.

Description

TECHNICAL FIELD [0001] The present invention relates to a pretreatment method, an analytical method, and a pretreatment apparatus for pretreating an analytical sample,

TECHNICAL FIELD The present invention relates to a pretreatment method of an analytical sample, a pretreatment analytical sample, an analytical method, and a pretreatment apparatus.

In the analysis of the sample, it is difficult to uniformly sample the sample because pretreatment by a physical method or a chemical method is performed and the sample itself contains a heterogeneous substance such as an emulsion in the pretreatment process, . Density differences between materials, such as W / O emulsions or O / W emulsions, result in the separation of samples due to gravity, so the reproducibility of the analysis drops over time.

When the matrix effect affects the analysis, as in the case of ICP analysis for measuring the metal content, due to the problem of the degree of separation of the sample, the sample itself is oxidized in an acid or air atmosphere to Ash to obtain a sample , And then dissolving it in an aqueous solution containing an acid is used. Such a method has a high risk of sampling and analysis due to the experimental conditions of acid and high temperature, and may cause loss of sample in the Ash work process. In addition, acid and the like may cause side effects of analytical inhibition, and errors of analysis results may occur depending on the skill of the experimenter.

 Even when measuring the water content using the Karl-Fisher method, the measurement results differ depending on the sampling time and position of the sample. For example, when dispersed by mechanical force, the degree of dispersion may be increased, but the reproducibility and accuracy of the analysis may be lower because the size limit of the resulting emulsion or droplet is larger than when ultrasound is used .

 In the case of a sample having a high viscosity material or a strong affinity with the sampling probe material and containing a component that causes deposition on the sampling probe, the sample is deposited on the sampling probe surface during the sampling process to form a film (fouling phenomenon). This has an influence on the concentration change in the sampling process. In particular, in the case of analyzing the low-concentration region band, it is an important factor that an error occurs. Since dozens of samples are collected and analyzed, May result in the dissolution of a film or deposited component in a later experimental sample analysis, which may affect the results of the analysis.

Alternatively, the dilution ratio may be maximized to minimize the effect on the analysis. However, this is because there is a limit to the dilution ratio because there is a numerical value of the analytical limit function for each analyzing device, and as the dilution ratio is increased, Can be increased.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method and an apparatus for analyzing an analyte, which can prevent deposition during sampling and / or analysis of analytes and induce uniform mixing of analytes, And a method for pre-processing the same.

The present invention provides an analytical sample pretreated with the pretreatment method of the analytical sample according to the present invention.

The present invention provides an analysis method using a pretreatment method of an analytical sample according to the present invention.

The present invention provides an automatic pretreatment apparatus for an analytical sample applied to a pretreatment method of an analytical sample according to the present invention.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to one aspect of the present invention,

Introducing the analytical sample into a pretreatment apparatus; And ultrasonically dispersing and dispersing the analytical sample in the pretreatment apparatus; Wherein the analytical sample comprises a W / O emulsion, a substance from which deposition occurs, or both.

According to one embodiment of the present invention, the analytical sample may be a hydrocarbon oil containing a W / O emulsion.

According to an embodiment of the present invention, the substance from which the deposition occurs is a solvent-insoluble substance, and the solvent insoluble substance includes at least one selected from the group consisting of asphaltenes, resins, and pitches , Hydrocarbon oil fraction.

According to one embodiment of the present invention, the step of dispersing comprises the steps of applying 0.1 w to 10 kW power and ultrasonic at a frequency of 0.1 KHz to 200 KHz for 0.1 second to 2 hours at a temperature above the freezing point and below the boiling point of the analytical sample Can be processed.

According to one embodiment of the present invention, the dispersing step may disperse the sample by ultrasonic treatment and mechanical stirring.

According to another aspect of the present invention,

To an analytical sample pretreated by a pretreatment method of the analytical sample according to the present invention.

According to another aspect of the present invention,

Introducing the analytical sample into a pretreatment apparatus; Ultrasonically treating and dispersing the analytical sample in the pretreatment apparatus; Sampling the sonicated analytical sample; And analyzing the sampled sample; Wherein the analytical sample comprises a W / O emulsion, a substance from which deposition occurs, or both.

According to an embodiment of the present invention, the analyzing step may be performed using an inductively coupled plasma (ICP), a liquid chromatography (LC), a liquid chromatography-mass spectrometry (LCMS), a high- (Total Organic Carbon), Total Nitrogen (TN), and Dissolved Total Nitrogen (KNO) are the most important factors in the determination of total nitrogen, And analyzing the sampled sample by at least one selected from the group consisting of analysis methods.

According to an embodiment of the present invention, the analysis method may have an analysis result of an average error rate within 2%.

According to yet another aspect of the present invention,

A sample receiving portion for pretreating the sample; An ultrasonic probe inserted into the sample accommodating portion and applying ultrasonic waves to disperse the sample; And a sample discharge pipe for discharging the sample from the sample storage part; To an automatic preprocessing apparatus for an analytical sample.

According to an embodiment of the present invention, the apparatus may further include a stirrer for mechanically stirring the sample of the sample storage portion.

According to an embodiment of the present invention, the apparatus may further include a temperature controller for controlling the temperature of the sample receiver.

According to an embodiment of the present invention, the ultrasonic probe may be configured such that ultrasonic waves of 0.1 to 10 kW power and 0.1 KHz to 200 KHz frequency are applied for 0.1 second to 2 hours at a temperature equal to or higher than the freezing point and the boiling point of the analytical sample The sample can be dispersed.

The present invention enables the production and sampling of samples that can induce uniform dispersion of molecules in a sample and provide reproducibility and accuracy of improved analysis by activating molecular motion in an analytical sample through ultrasonic treatment.

The present invention can significantly reduce the amount of the sample compared with mechanical blending using the existing blender, and make it possible to produce and sample a uniform sample in a short time.

The present invention solves the problem due to sample deposition that may occur in the sampling probe and enables analysis and measurement of the low concentration region band.

The present invention can be applied to the sampling of analytical samples of various analytical devices (Karl-Fisher, ICP, chromatography, etc.) to improve the accuracy and reproducibility of the analysis.

FIG. 1 is a flow chart illustrating a method of pre-processing an analytical sample of the present invention, according to an embodiment of the present invention.
Figure 2 illustrates a flow diagram of an analytical method of the present invention, in accordance with an embodiment of the present invention.
Figure 3 illustrates, by way of example, a cross-section of a pretreatment apparatus of the present invention, in accordance with one embodiment of the present invention.
4 shows an analysis result of a sample sampled according to the third embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Also, terminologies used herein are terms used to properly represent preferred embodiments of the present invention, which may vary depending on the user, intent of the operator, or custom in the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.

The present invention relates to a method for pre-processing an analytical sample. According to an embodiment of the present invention, a pre-processing method of the analytical sample is capable of preparing and sampling a uniform sample for analysis, It is possible to prevent the sample deposition inside and improve the accuracy and reproducibility of the analysis. In addition, the amount of time and sample for sample or sample production can be greatly reduced.

FIG. 1 is a flowchart illustrating a preprocessing method of an analytical sample according to an embodiment of the present invention.

According to an embodiment of the present invention, referring to FIG. 1, the preprocessing method includes the steps of (110) introducing an analysis sample into a preprocessor; And ultrasonically dispersing (120) the analytical sample in the pretreatment apparatus; . ≪ / RTI >

In one embodiment of the present invention, introducing (110) an analytical sample into a pretreatment device may introduce a W / O emulsion, a substance from which deposition occurs, or an analytical sample containing both, into the pretreatment device.

For example, the analytical sample containing the W / O emulsion may be a hydrocarbon oil fraction comprising a W / O (water-in-oil) emulsion, and the hydrocarbon oil fraction may be light oil, heavy oil or the like.

For example, the substance from which deposition occurs is a solvent-insoluble substance, for example, a high viscosity hydrocarbon oil fraction containing at least one selected from the group consisting of asphaltene, resin and pitch contained in heavy oil .

For example, introducing the analytical sample into the pretreatment apparatus 110 may include introducing an analytical sample diluted in the analytical sample stock solution or a diluting solvent, or introducing an analytical sample diluted in the diluting solvent into the analytical sample stock solution or diluted analytical sample introduced into the pretreatment apparatus Can be added to dilute.

For example, the diluent solvent may be contained in an amount of more than 0 parts by weight and 99 parts by weight based on 100 parts by weight of the entire analytical sample.

In one embodiment of the present invention, dispersing (120) comprises: a temperature above the freezing point and below the boiling point of the analytical sample, or the analytical sample diluted with the diluting solvent; For example from -10 DEG C to 100 DEG C; 0 DEG C to 90 DEG C; From 5 ° C to 70 ° C or from 10 ° C to 60 ° C, from 0.1w to 10kW; Or 1 kW to 8 kW power and 0.1 KHz to 100 KHz; 1 KHz to 70 KHz; Alternatively, the analytical sample can be dispersed by ultrasonication at a frequency of 5 KHz to 50 KHz. Also, the dispersing step 120 may be performed for a period of from 0.1 second to 2 hours; 1 minute to 100 minutes; 1 minute to 1 hour; Or sonication for 1 to 30 minutes. When included within the above range of temperature, frequency and intensity, it is possible to form a small and uniform emulsion in a much shorter time than the mechanical method through ultrasonic treatment, to improve the emulsion dispersion in the sample, have.

For example, an analytical sample containing a W / O emulsion can increase the motion of a molecule using ultrasonic waves to reduce the size of the emulsion produced, uniformize the size distribution and number density of the emulsion, The dispersibility of the emulsion due to the action can be increased. In addition, the accuracy of the analysis result can be improved by increasing the uniformity of the sample.

For example, an analytical sample containing a substance causing deposition may induce molecular motion using ultrasonic waves to prevent fouling or deposition on the surface of the sampling probe, thereby reducing the error range of the analysis process and improving the accuracy of the analysis .

For example, the dispersing step 120 may include dispersing the sample by applying ultrasonic treatment and mechanical agitation together to prevent hot spots during preprocessing of analytical samples of high viscosity.

As an example of the present invention, an analytical sample pretreated with the pretreatment method can be provided. The analytical sample improves the reproducibility and accuracy of the analysis and can provide uniform analysis results in a low concentration and a high concentration range.

The present invention relates to an analytical method using the pretreatment method of the present invention. According to an embodiment of the present invention, the analytical method is a method of analyzing a uniformly dispersed sample Production and sampling can be performed, and the accuracy, accuracy and reproducibility of analysis results can be improved.

Figure 2 illustrates a flow diagram of an analytical method of the present invention, in accordance with an embodiment of the present invention.

According to one embodiment of the present invention, referring to FIG. 2, the analyzing method includes the steps of: (210) introducing an analytical sample into a pretreatment apparatus; Ultrasonically dispersing (220) the analytical sample in the pretreatment apparatus; Sampling (230) the sonicated analytical sample; And analyzing (240).

In one embodiment of the present invention, the method includes the steps of: (210) introducing an analytical sample into a pretreatment apparatus; The step 220 of sonicating and dispersing the analytical sample in the pretreatment apparatus is as described above.

In one embodiment of the present invention, the step 230 of sampling the ultrasonic treated analytical sample is a step of preparing or sampling the analytical sample pretreated by the ultrasonic treatment according to the analytical method. The production and sampling of these samples can be appropriately selected according to the analysis method.

For example, the analysis may be performed using an ICP (inductively coupled plasma), an LC (liquid chromatography) method, (Liquid chromatography-mass spectrometry), High-performance liquid chromatography (HPLC), Gel permeation chromatography (GC), Gas chromatography, Gas chromatograph-mass spectrometry, Karl-Fisher method, Total Organic Carbon, Total Nitrogen (TN), and Dissolved Total Nitrogen (ANOVA).

As an example of the present invention, the analysis method can reduce the sample preparation time and the sampling time, and can prevent the uniformity of the sample and the deposition of the sample in the analysis process. Therefore, it is possible to provide an analysis result of an average error rate of less than 2% have.

The present invention relates to an automatic pretreatment apparatus for an analytical sample, and it is possible to sample and sample an analytical sample containing an emulsion and / or a high viscosity within a short time.

3 is a cross-sectional view of an automatic pretreatment apparatus for an analytical sample according to an embodiment of the present invention.

3, the automated preprocessing apparatus for an analytical sample includes: a sample receiving unit 310 for pretreating a sample; An ultrasonic probe 320 which is inserted into the sample storage part 310 and disperses the sample by applying ultrasonic waves; And a sample discharge pipe 340 for discharging the sample from the sample storage part 310; . ≪ / RTI >

In one example of the present invention, the sample accommodating portion 310 is made of a material not reacting with the analytical sample and may include, for example, stainless steel or the like. Further, a transparent material such as a transparent polymer, a glass material, or the like may be used to confirm the pretreatment process of the analytical sample.

Since the ultrasonic probe 320 is inserted into the sample accommodating portion 310 and can be moved up and down and left and right, the ultrasonic probe 320 can provide uniform ultrasonic waves according to the amount, component, etc. of the analytical sample.

For example, the ultrasonic probe 320 may further include a rotatable single or a plurality of rotating blades (not shown) to mechanically stir the ultrasonic probe 320 with a rotating blade while applying ultrasonic waves.

For example, the rotary vanes may be mounted in a plurality of rows and sequentially mounted along the height of the probes.

For example, the ultrasonic probe 320 exists singly or plurally, and may be inserted at the upper end of the sample accommodating portion 310 or inserted into the side surface or the bottom surface of the sample accommodating portion 310.

For example, the ultrasonic probe 320 may be configured to measure the temperature of the analytical sample or the analytical sample diluted with the diluting solvent at a temperature above the freezing point and below the boiling point; For example from -10 DEG C to 100 DEG C; 0 DEG C to 90 DEG C; From 5 ° C to 70 ° C or from 10 ° C to 60 ° C at a power of from 0.1 w to 10 kW; Or 1 kW to 8 kW power and 0.1 KHz to 100 KHz; 1 KHz to 70 KHz; Or an ultrasonic wave having a frequency of 5 KHz to 50 KHz can be applied.

In an example of the present invention, the sample inlet pipe 330 can inject the analytical sample into the sample receiving portion 310.

As an example of the present invention, the sample discharge pipe 340 may be directly connected to the sampling probe of the analyzer or may discharge the sample to a device or a container for sample preparation and sampling.

In one embodiment of the present invention, the sample storage part 310 includes an agitator 350 for mechanically stirring the sample; As shown in FIG.

The sample accommodating portion 310 may further include a temperature adjusting device (not shown) capable of adjusting the temperature of the sample accommodating portion 310. The sample accommodating portion 310 may be mounted in an outer wall 360 of the sample accommodating portion 310 . For example, the outer wall 360 may constitute a heat insulator having a constant thickness to protect the sample accommodating portion 310 and maintain the temperature.

In one embodiment of the present invention, the sample receiving portion 310 may further include a top-openable cap for sealing the sample receiving portion 310 to prevent contact of the analytical sample with air, , A transparent polymer, glass, or a stainless steel material.

As an example of the present invention, an automatic preprocessing apparatus for an analytical sample according to the present invention may be installed in a sampling apparatus or an analyzing apparatus.

Example 1

Moisture content measurement of hydrocarbon oil containing W / O emulsion

Three samples were prepared by mixing hydrocarbon oil and water at a mass ratio of 95: 5. The water content was measured after pretreatment as follows. The results are shown in Table 1.

Sample A

After mixing for 10 minutes using a vortex mixer, the vials were sampled through an autosampler and water content was measured.

Sample B

The mixed sample was sampled through an autosampler while mixing with a magnetic bar and a magnetic stirrer for 10 minutes, and moisture content was measured.

Sample C

The mixed sample was sampled using an autosampler according to the present invention while dispersing the emulsion (1 minute) using ultrasonic waves, and moisture content was measured.

sample Measured average moisture content
(%) Measured maximum value
(%) Measurement minimum
(%) A 3.9 3.49 4.31 B 3.5 2.97 4.03 C 4.7 4.63 4.77

As shown in Table 1, it can be seen that the accuracy of the ultrasound-treated sample C is significantly improved compared to the samples A and B.

Example 2

Using metal content measurement (ICP-AES) of hydrocarbon oil containing W / O emulsion (analysis based on ASTM D7691)

Three samples of the hydrocarbon oil fraction (100 ppm of Ca concentration) and water were mixed at a ratio of 90:10 in mass ratio were pretreated and sampled, and the metal content was measured 10 times. The results are shown in Table 2. Xylene was used as a diluent.

Sample A

After mixing for 10 minutes using a vortex mixer, the contents of the vials were sampled through an autosampler and the Ca content was measured. The results are shown in Table 2.

Sample B

The mixed sample was sampled through an autosampler while mixing with a magnetic bar and a magnetic stirrer for 10 minutes, and the Ca content was measured.

Sample C

The mixed samples were sampled using an autosampler according to the present invention while dispersing the emulsion (1 minute) using ultrasonic waves, and then the Ca content was measured.

sample Measured average Ca content
(ppm) Measured maximum value
(ppm) Measurement minimum
(ppm) A 86 82 90 B 87 81 93 C 92 91 93

As shown in Table 2, it can be seen that the accuracy of the ultrasound-treated sample C is significantly improved compared to the samples A and B.

Example 3

(Based on ASTM D7691) using metal content measurement (ICP-AES) on hydrocarbon oils (heavy oil, Castilla Crude, V content 146ppm)

The three samples with hydrocarbon fractions containing heavy asparten (heavy oil, Castilla Crude, V content 146ppm) were pretreated and sampled respectively, and then the V content was measured 20 times, and the tendency according to the number of measurements was measured. 4. Xylene was used as a diluent.

Sample A

After mixing for 10 minutes using a vortex mixer, the sample was sampled through an autosampler in a vial and the V content was measured.

Sample B

The mixed samples were sampled through an autosampler while mixing with a magnetic bar and a magnetic stirrer for 10 minutes, and the V content was measured.

Sample C

The mixed sample was sampled using an autosampler according to the present invention while dispersing it using ultrasonic waves (for 1 minute), and then the V content was measured.

Referring to FIG. 4, it is confirmed that the sample C pretreated with the ultrasonic wave by the method of the present invention provides uniform analysis results in 20 times of the samples A and B analysis. This is because the analytical sample treated by the pretreatment method according to the present invention provides a homogeneous analysis result by raising the homogeneity of the analytical object V contained in the asphaltene.

Experimental Example 4

Measurement and Reproducibility of Metal Content of Hydrocarbons Containing Asparten (Heavy Oil, Castilla Crude)

1 ppm, 2 ppm and 4 ppm samples prepared by diluting a 3 wt% calcium naphthate reagent with hydrocarbon oil (Castilla Crude) containing asphaltene in large amounts were pre-treated , The metal content was measured 10 times for the same sample, and the average error rate with respect to the analysis result was calculated and shown in Table 3.

The metal content was measured using ICP-AES and using xylene as a diluent based on ASTM D7691.

Sample A.

 After mixing for 10 minutes using a vortex mixer, the contents of the vials were sampled through an autosampler and the Ca content was measured.

Sample B.

The mixed sample was sampled through an autosampler while mixing with a magnetic bar and a magnetic stirrer for 10 minutes, and the Ca content was measured.

Sample C.

The mixed sample was sampled using an autosampler according to the present invention while dispersing it using ultrasonic waves (for 1 minute), and then the Ca content was measured.

sample Average error rate A 5.2% B 7.3% C 1.4%

Table 3 shows that the reproducibility of the sample C pretreated with the ultrasonic wave by the method according to the present invention is much improved compared to the samples A and B.

The present invention relates to an analytical sample capable of producing and sampling a sample having a good degree of dispersion and / or homogeneity of an analytical object by applying a pretreatment step of an analytical sample using ultrasonic waves and capable of improving the accuracy and reproducibility of analytical results A pretreatment method of the present invention, an analytical sample pretreated by the method, an analysis method using the same, and a pretreatment device.

Claims (13)

Introducing the analytical sample into a pretreatment apparatus; And
Ultrasonically treating and dispersing the analytical sample in the pretreatment apparatus;
Lt; / RTI >
Wherein the analytical sample comprises a W / O emulsion, a substance from which deposition occurs, or both.
The method according to claim 1,
Wherein the analytical sample is a hydrocarbon oil comprising a W / O emulsion.
The method according to claim 1,
Wherein the material from which the deposition occurs is a solvent insoluble material and the solvent insoluble material is a hydrocarbon oil fraction containing at least one selected from the group consisting of asphaltenes, Pretreatment method.
The method according to claim 1,
The ultrasonic treatment step may comprise applying ultrasonic waves at a frequency of 0.1 to 10 kW and a frequency of 0.1 to 200 KHz at a temperature above the freezing point and below the boiling point of the analytical sample
Wherein the sample is treated for from 0.1 second to 2 hours.
The method according to claim 1,
Wherein the dispersing step comprises dispersing the sample by ultrasonic treatment and mechanical stirring.
An analytical sample pretreated by the method of any one of claims 1 to 5.
Introducing the analytical sample into a pretreatment apparatus;
Ultrasonically treating and dispersing the analytical sample in the pretreatment apparatus;
Sampling the sonicated analytical sample; And
Analyzing the sampled sample;
Lt; / RTI >
Wherein the analytical sample comprises a W / O emulsion, a substance from which deposition occurs, or both.
8. The method of claim 7,
The analyzing step may be performed using an inductively coupled plasma (ICP), a liquid chromatography (LC), a liquid chromatography-mass spectrometry (LCMS), a high performance liquid chromatography (HPLC), a gel permeation chromatography (GPC) Gas chromatograph-mass spectrometry, Karl-Fisher method, total organic carbon (TOC), total nitrogen (TN), and dissolved total nitrogen ≪ / RTI > analyzing said sampled sample by said analyzer.
8. The method of claim 7,
Wherein the analysis method has an analysis result of an average error rate of 2% or less.
A sample receiving portion for pretreating the sample;
An ultrasonic probe inserted into the sample accommodating portion and applying ultrasonic waves to disperse the sample; And
A sample discharge pipe for discharging the sample from the sample storage portion;
/ RTI >
Automatic preprocessing equipment for analytical samples.
11. The method of claim 10,
And a stirrer for mechanically stirring the sample of the sample accommodating portion.
Automatic preprocessing equipment for analytical samples.
11. The method of claim 10,
And a temperature control device for controlling the temperature of the sample storage part.
11. The method of claim 10,
Wherein the ultrasonic probe disperses the sample by applying a power of 0.1 w to 10 kW and an ultrasonic wave of a frequency of 0.1 KHz to 200 KHz for 0.1 second to 2 hours at a temperature equal to or higher than the freezing point and the boiling point of the analytical sample, Automatic preprocessing equipment for samples.

Images