JP3772597B2 - Peroxide analysis method and apparatus - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a peroxide analysis method and apparatus for measuring hydrogen peroxide and other peroxides contained in an organic solvent by a reverse micelle media chemiluminescence method, and more particularly, a hydrogen peroxide and other peroxides measured by flow injection analysis (FIA). The present invention relates to an oxide analysis method and apparatus.
[0002]
[Prior art]
Conventionally, hydrogen peroxide contained in an organic solvent is obtained by once extracting hydrogen peroxide in an organic solvent solution from an organic solvent phase into an aqueous phase using water or the like, and then adding excess hydrogen contained in the aqueous phase. Hydrogen oxide is measured by a method such as an FIA method using chemiluminescence or an electrochemical method in which it is converted into oxygen for measurement.
However, in such a measuring method, since the extraction operation takes time, the rapidity of chemiluminescence is lost, and the extraction rate of hydrogen peroxide fluctuates, making it impossible to perform quantification with high sensitivity. There is a problem.
[0003]
As a measurement method for improving such a point, by using a reverse micelle media chemiluminescence method, a sample solution comprising an organic solvent containing hydrogen peroxide and a reverse micelle solution containing luminol and a base in the inner aqueous phase of the reverse micelle are used. There has been proposed a method for measuring hydrogen peroxide in which a reagent solution is contacted and the light that is chemiluminescent at this time is measured. According to this method, hydrogen peroxide contained in an organic solvent can be measured directly and quickly without extracting it into the aqueous phase, and high-sensitivity and high-reliability measurement is possible at low cost. It is.
[0004]
According to this method, hydrogen peroxide contained in an organic solvent can be continuously measured by flow injection analysis. A method and apparatus for automatically collecting a sample from a process for analysis. Is desired.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to extract a sample from a process directly and quickly without extracting the peroxide contained in the organic solvent into an aqueous phase, and to measure it directly and quickly, and at a low cost, high sensitivity, The object is to propose a method and apparatus for analyzing peroxides that can automatically perform highly reliable measurements.
[0006]
[Means for Solving the Problems]
The present invention is the following peroxide analysis method and apparatus.
(1) A method in which a reagent solution containing a reverse micelle of a luminescent reagent is reacted with a peroxide contained in an organic solvent, and the peroxide is analyzed by a reverse micelle media chemiluminescence method,
In the sampling device, a certain amount of sample is taken from the process by the sampling valve, diluted with a diluent measured by the second metering valve to prepare a diluted sample, and the second and third metering valves and the detector in the measuring device. The carrier solution is fed through, the reagent solution weighed by the first metering valve is injected into the carrier fluid channel, and the diluted sample prepared by the sampling device is metered by the third metering valve and injected into the carrier fluid channel. React with reagent solution and detect luminescence with detector
Peroxide analysis method.
(2) The method according to (1) above, wherein the diluted sample prepared in the sampling device is sent to the measuring device with a carrier liquid.
(3) In the measuring device, the carrier liquid is sent through the second to third metering valves and the detector, the reagent solution metered by the first metering valve is injected into the carrier liquid channel, and metered by the fourth metering valve. The reference liquid is injected into the carrier liquid flow path, the light emission amount of the reference liquid is detected by a detector, and the peroxide concentration of the sample is calculated from the relational expression between the light emission amount of the reference liquid and the light emission amount of the sample (1 ) Or (2).
(4) An apparatus for analyzing a peroxide by a reverse micelle media chemiluminescence method by reacting a reagent solution containing reverse micelles of a luminescent reagent with a peroxide contained in an organic solvent,
A sampling device for taking a fixed amount of sample from the process by the sampling valve and diluting with a diluent measured by the first metering valve to prepare a diluted sample;
A carrier liquid flow path is formed through the bypass path of the second and third metering valves having a metering path and a bypass path and a detector, and a reagent solution measured in the metering path of the second metering valve is injected into the carrier liquid flow path. And a measuring device for measuring the amount of luminescence with a detector by measuring the diluted sample prepared by the sampling device through the measuring channel of the third measuring valve, injecting it into the carrier liquid channel and reacting with the reagent solution.
Peroxide analysis device containing.
(5) The method according to (4) above, wherein the sampling device has means for sending the prepared diluted sample to the measuring device with a carrier liquid.
(6) The measuring device sends the carrier liquid through the bypass passages of the second to fourth metering valves and the detector, injects the reagent solution metered in the metering passage of the first metering valve into the carrier fluid channel, 4 is configured to inject the reference liquid measured by the measuring path of the metering valve 4 into the carrier liquid flow path and detect the light emission amount of the reference liquid with a detector. The apparatus according to (4) or (5), further including a control device that calculates the peroxide concentration of the sample from the relational expression.
(7) The sampling valve has a system for collecting a certain amount of sample from the process, and a dilution chamber for preparing the diluted sample by introducing and mixing the collected sample and the diluent measured by the first metering valve. The apparatus according to any one of (4) to (6) above.
(8) The apparatus according to (7), wherein the sampling device has means for introducing and stirring gas into the dilution chamber.
(9) The apparatus according to (6), further comprising means for introducing a gas into a path for sending the diluted sample prepared by the sampling apparatus to the measuring apparatus using a carrier liquid and discharging the liquid in the system.
[0007]
In the present invention, the peroxide to be measured is a peroxide contained in an organic solvent, and an organic solvent containing a peroxide prepared by dissolving or diluting a sample is used as the sample solution.
As the peroxide, any peroxide that can be dissolved or dispersed in an organic solvent, such as hydrogen peroxide or organic peroxide, can be measured without limitation, but hydrogen peroxide is particularly suitable as a measuring object.
[0008]
The organic solvent of the sample solution is preferably a low polarity organic solvent, specifically, toluene, orthoxylene, benzene, n-octane, n-hexane, cyclohexane or a mixture thereof. Further, although the emission intensity of chemiluminescence is reduced, organic solvents having a little polarity, specifically diethyl ether, chloroform, tetrahydrofuran, or a mixture thereof can be used. Furthermore, although the emission intensity of chemiluminescence is considerably reduced, organic solvents having a relatively high polarity, specifically, dichloromethane, acetone, ethanol or a mixture thereof can be used. When peroxide is contained in the organic solvent having a relatively high polarity, the intensity of chemiluminescence is considerably reduced, but the emission intensity is higher than that of a control (blank) containing no peroxide. Oxide measurements are possible.
[0009]
The concentration of peroxide in the sample solution at the time of measurement was 1.2 × 10 in the case of hydrogen peroxide. ^-7 M-3x10 ^-Five M, preferably 2.4 × 10 ^-7 M ~ 0.6 × 10 ^-Five When the sample solution to be measured has a high hydrogen peroxide concentration, it can be diluted with a diluting solution composed of the organic solvent so as to be in the above range to obtain a sample solution.
[0010]
As a luminescent reagent used for measurement in the present invention, any reagent capable of emitting light by reacting with a peroxide can be used without limitation, and examples thereof include luminol, lucigenin, and lophine. Among these, luminol is preferable because it is stable and has high emission intensity.
[0011]
The reagent solution used in the present invention is a reverse micelle solution containing a luminescent reagent such as luminol and a base in the inner aqueous phase of the reverse micelle. Reverse micelles can be formed by a known method, for example, by dispersing or solubilizing a small amount of water in a very polar organic solvent using a surfactant. Specifically, it can be formed by dispersing a small amount of a basic luminol aqueous solution in an organic solvent containing a surfactant.
[0012]
Examples of extremely low polarity organic solvents (hereinafter sometimes referred to as bulk organic solvents) used for the formation of reverse micelles include chloroform, cyclohexane, and mixtures thereof. Among these, a mixed liquid having a volume ratio of chloroform and cyclohexane of 6: 5 or cyclohexane is preferable.
[0013]
Examples of the surfactant used for forming the reverse micelle include cationic surfactants such as cetyltrimethylammonium chloride (hereinafter sometimes abbreviated as CTAC) and cetyltrimethylammonium bromide. Further, hexanol or alcohol having a chain length longer than that can be used as an auxiliary surfactant.
[0014]
FIG. 2 is a schematic diagram of the structure of the reverse micelle, in which 1 is a reverse micelle and 2 is a surfactant constituting the reverse micelle. The reverse micelle 1 has a structure in which the inner aqueous phase 3 surrounded by the surfactant 2 is dispersed in the bulk solvent 4, and at this time, the hydrophilic group 2 a of the surfactant 2 has an inner aqueous phase (water) inside the reverse micelle 1. Pool) 3 and the hydrophobic group 2b is directed to the outer bulk solvent 4 (commonly referred to as organic phase, sometimes referred to as bulk organic phase) 4.
[0015]
The inner aqueous phase of the reverse micelle used as the reagent solution in the present invention contains a luminescent reagent such as luminol and a base. In the case of luminol, the concentration of the luminescent reagent is 0.01 M to 0.04 M, preferably around 0.02 M as the concentration in the basic luminol aqueous solution dispersed in the bulk organic solvent containing the surfactant as the inner aqueous phase of the reverse micelle. It is desirable.
[0016]
As the base contained in the inner aqueous phase of the reverse micelle, those capable of supplying hydroxide ions can be used without limitation, but sodium carbonate or sodium hydroxide is preferable, and a mixed liquid of chloroform and cyclohexane is particularly preferable as a bulk organic solvent. When using, sodium carbonate is preferable, and when using hexane containing hexanol, sodium hydroxide is preferable.
The concentration of the base in the reagent solution is 0.6M to 1M, preferably around 0.8M, as the concentration in the basic luminol aqueous solution dispersed in the bulk organic solvent containing the surfactant as the inner aqueous phase of the reverse micelle. desirable.
[0017]
A specific reagent solution used in the present invention is a reverse micelle solution formed using cyclohexane as a bulk solvent, hexanol as an auxiliary surfactant, and cetyltrimethylammonium chloride as a surfactant. Examples include those containing luminol and a base in the inner aqueous phase of the reverse micelle in the solution. When such a reagent solution using cyclohexane as a bulk solvent is used, the detection limit of hydrogen peroxide in the sample solution is 1.2 × 10 6. ^-7 About M.
[0018]
Another reagent solution is a reverse micelle solution in which a mixed solution of chloroform and cyclohexane, for example, a mixed solution with a volume ratio of 6: 5 is used as a bulk solvent and cetyltrimethylammonium chloride is formed as a surfactant. Examples include those containing luminol and a base in the inner aqueous phase of the reverse micelle in the solution. When a reagent solution using such a mixed solution of chloroform and cyclohexane as a bulk solvent is used, the detection limit of hydrogen peroxide in the reagent solution is 2.5 × 10 6. ^-7 About M.
[0019]
In the present invention, chemiluminescence proceeds using such reverse micelles as a reaction field. In the case of luminol, chemiluminescence is generated by reacting with hydrogen peroxide in the presence of hydroxide ions and being oxidized to 3-aminophthalate. This reaction is illustrated in FIG. That is, hydrogen peroxide enters the inner aqueous phase of the reverse micelle, and this hydrogen peroxide reacts with luminol in the presence of hydroxide ions to oxidize to 3-aminophthalate to emit light.
[0020]
In the present invention, the sample solution and the reagent solution are brought into contact with each other, and the chemiluminescent light is measured at this time, so that hydrogen peroxide contained in the organic solvent is directly and automatically extracted without being extracted into the aqueous phase. Can be measured. In the present invention, the hydrogen peroxide concentration can be quantified by the emission intensity. For example, from the relational expression between the light emission amount of the reference solution and the light emission amount of the sample, or by preparing a calibration curve by measuring the light emission intensity of a hydrogen peroxide solution of a known concentration in advance, The concentration can be quantified. The presence or absence of hydrogen peroxide can also be determined.
[0021]
The peroxide analysis method and apparatus of the present invention utilizes the measurement method as described above. The analyzer of the present invention comprises a sampling device for collecting a sample from a process to prepare a diluted sample, and a measuring device for measuring the diluted sample by reverse micelle media chemiluminescence.
The sampling device in the peroxide analyzer of the present invention is configured to prepare a diluted sample by collecting a predetermined amount of sample from the process by the sampling valve and diluting with a diluent measured by the first metering valve. Is done. The sampling device preferably has means for sending the prepared diluted sample to the measuring device using a carrier liquid. In this case, it is preferable that the sampling apparatus has means for introducing a gas into a path for sending the prepared diluted sample to the measuring apparatus with a carrier liquid and discharging the liquid in the system.
[0022]
The sampling valve preferably has a system for collecting a certain amount of sample from the process, and a dilution chamber for preparing the diluted sample by introducing and mixing the collected sample and the diluent measured by the first metering valve. . In this case, the sampling device preferably has means for introducing gas into the dilution chamber and stirring.
[0023]
The measuring device forms a carrier liquid flow path through the bypass path of the second and third metering valves having a metering path and a bypass path and a detector, and the reagent solution metered in the metering path of the second metering valve is supplied to the carrier liquid flow. The diluted sample prepared by the sampling device is weighed by the metering channel of the third metering valve, injected into the carrier liquid channel and reacted with the reagent solution, and the amount of luminescence is detected by the detector. Is done. The detector has a flow cell and is configured to detect luminescence due to the reaction between the luminescent reagent and the sample.
[0024]
The measuring device sends the carrier liquid through the bypass passages of the second to fourth metering valves and the detector, injects the reagent solution metered by the metering channel of the first metering valve into the carrier channel, and the fourth metering device. It is configured to inject the reference liquid measured in the valve measurement path into the carrier flow path and detect the light emission amount of the reference liquid with a detector. From the relational expression between the light emission amount of the reference liquid and the light emission amount of the sample, It is preferable to have a control device that calculates the peroxide concentration.
[0025]
In the method for analyzing peroxide according to the present invention, a predetermined amount of a sample is collected from a process by a sampling valve in a sampling device, diluted with a diluent measured by a first measuring valve, and a diluted sample is prepared. The carrier liquid is sent through the second and third metering valves and the detector, the reagent solution metered by the second metering valve is injected into the carrier liquid channel, and the diluted sample prepared by the sampling device is metered by the third metering valve. Then, it is injected into the carrier liquid channel and reacted with the reagent solution, and the amount of luminescence is detected by a detector to analyze the peroxide.
[0026]
The diluted sample prepared in the sampling device can be sent to the measuring device with the carrier liquid.
In the measuring device, the carrier liquid is sent through the second to third metering valves and the detector, the reagent solution weighed by the first metering valve is injected into the carrier liquid channel, and the reference liquid weighed by the fourth metering valve is used. By injecting into the carrier liquid flow path, the light emission amount of the reference solution is detected by a detector, and the peroxide concentration of the sample can be calculated from the relational expression between the light emission amount of the reference solution and the light emission amount of the sample.
[0027]
By injecting a base before injecting the sample solution and allowing it to be adsorbed to the flow cell, the adsorption and reaction of the sample and the reagent can be promoted, and therefore a base injection means can be provided. However, if the reagent solution contains a base, the base is adsorbed on the flow cell by repeating the measurement, and the measurement accuracy is increased.
[0028]
For reverse micelle media chemiluminescence by FIA, the mechanism schematically shown in FIG. 4 is assumed. First, reverse micelles containing a base are adsorbed on the glass surface of the flow cell to cover the cell surface. Next, the hydrogen peroxide in the injected toluene is taken into the state where the surface treatment has been performed, and remains on the glass surface. Luminol in reverse micelles injected thereafter enters this microreaction field, and light emission occurs. This luminol is probably hardly adsorbed. When there is no surfactant, that is, when adsorbed in the form of an aqueous solution, it is presumed that toluene is less likely to contact the surface and hydrogen peroxide is less likely to be taken into the microreaction field.
[0029]
【The invention's effect】
According to the present invention, the sample is collected from the process with the sampling device and diluted, and the peroxide is measured by the reverse micelle media chemiluminescence method with the measuring device, so that the peroxide contained in the organic solvent is measured. It is possible to directly and quickly measure a sample from a process without extracting an object into an aqueous phase, and it is possible to automatically perform measurement at low cost, high sensitivity and high reliability.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
FIG. 1 is a flow chart of a peroxide analyzer according to an embodiment of the present invention, and shows an example of an apparatus for analyzing hydrogen peroxide by the FIA method using luminol as a luminescent reagent.
[0031]
In FIG. 1, reference numeral 10 denotes a sampling device, which includes a sampling valve 11, a metering valve M1, a diluent tank 13, a transport liquid tank 14, and switching valves V1 to V5. The sampling valve 11 includes a stem 11a for collecting a certain amount of sample from the test object 16 flowing in the process 15, and a dilution chamber 11b for diluting the collected sample, but detailed illustration is omitted.
[0032]
The metering valve M1 is configured such that the rotor R1 having the metering path A1 and the bypass path B1 rotates to switch the flow path. The switching valves V1 to V5 are three-way valves having ports a, b, and c, respectively. A diluent 17 such as toluene is stored in the diluent tank 13. A carrier liquid such as acetone, water, or a mixture thereof is stored in the carrier liquid tank 14.
[0033]
20 is a measuring device, and measuring passages A2, A3, A4 having the same configuration as the measuring valve M1, bypass passages B2, B3, B4, measuring valves M2, M3, M4 having rotors R2, R3, R4, a detector 21, It comprises a carrier liquid tank 22, a reagent solution tank 23, a reference liquid tank 24, a drain tank 25, and switching valves V6 to V8. Reference numeral 27 denotes a control device. The detector 21 is configured to detect in the flow cell the luminescence intensity due to the reaction between the sample and the luminescent reagent by the FIA method.
[0034]
A carrier liquid 28 such as toluene is stored in the carrier liquid tank 22. The reagent solution tank 23 stores a reagent solution 29 made of a reverse micelle solution containing luminol and a base as a luminescent reagent. A reference liquid 30 containing a predetermined amount of hydrogen peroxide is stored in the reference liquid tank 24. A drainage 31 is stored in the drainage tank 25. The switching valves V6 to V8 are three-way valves having the same configuration as the switching valves V1 to V5.
[0035]
In the method for analyzing hydrogen peroxide by the above apparatus, the sample sampled from the process 15 in the sampling apparatus 10 is diluted by the instruction of the control apparatus 27 and sent to the measuring apparatus 20, and this diluted sample is reacted with the reagent solution 29. The detection unit 21 detects the emission intensity, inputs the detection signal to the control device 27, and records and outputs the analysis value.
[0036]
Sampling in the sampling device 10 is performed as follows. First, the rotor R1 of the metering valve M1 is rotated to connect the metering path A1 to the lines L1 and L2 as shown by the solid line in FIG. 1, and the pump P1 is driven to drive the diluent from the diluent tank 13 through the lines L1 and L2. 17 is circulated and weighed in the measuring path A1. On the other hand, in the sampling valve 11, a certain amount of the test object 16 is collected from the process 15 as a sample by the stem 11a.
[0037]
Subsequently, the rotor R1 of the metering valve M1 is rotated to connect the metering path A1 to the lines L4 and L5 (bypass path B1 is connected to L1 and L2) to stop the pump P1. The switching valve V1 is switched to ports b and c, the switching valve V2 is switched to ports a and b, and the switching valve V3 is switched to ports a and b. As a result, the gas supplied from the gas supply source G is supplied to the metering valve M1 through the line L3, the switching valve V2 (a, b), and the line L4. As a result, the diluent in the metering path A1 is sent to the dilution chamber 11b of the sampling valve 11 through the line L5, the switching valve V3 (a, b), and the line L6. Here, the sample collected by the stem 11a is diluted by injecting it into the diluent, and the diluted sample is stirred by further flowing gas to dissolve the sample. The exhaust gas is discharged out of the system through the line L7 and the switching valve V1 (b, c).
[0038]
Next, the switching valve V5 is switched to the ports b and c, the pump P2 is driven, the carrier liquid 18 is circulated from the carrier liquid tank 14 through the lines L8 and L9, and the bubbles in the lines L8 and L9 are removed. Further, the switching valve V2 is switched to ports b and c to shut off the gas, and the metering path A1 of the metering valve M1 is opened to the atmosphere.
[0039]
Then, the switching valve V5 is switched to the ports a and b, the switching valve V4 is switched to the ports b and c, the switching valve V1 is switched to the ports a and b, and the switching valve V3 is switched to the ports b and c. 18 is sent to the dilution chamber 11b of the sampling valve 11 through the line L9, the switching valve V5, the line L11, the switching valve V4, the line L12, and the switching valve V1, and the diluted sample in the dilution chamber 11b is sent to the line L6, the switching valve V3, and the line L13. To the measuring device 20.
[0040]
In the measuring device 20, the pump P3 is driven in the state of the solid lines of the metering valves M2, M3, and M4 and in the state where the switching valve V6 is switched to the ports b and c. As a result, the carrier liquid 28 flows from the carrier liquid tank 22 to the line L21, the bypass path B2 of the metering valve M2, the line L22, the bypass path B3 of the metering valve M3, the line L23, the bypass path B4 of the metering valve M4, the line L24, and the detector 21. , Circulates through line L25, switching valve V6 (b, c), line 26.
[0041]
On the other hand, the pump P4 is driven in a state where the switching valve V7 is switched to the ports b and c, and the reagent solution 29 is moved from the reagent solution tank 23 to the line L27, the measuring path A2 of the measuring valve M2, the line L28, and the switching valve V7 (b, c) Feed through the line L29 and stop after driving the pump P4 for 1 minute. Further, the pump P5 is driven in a state where the switching valve V8 is switched to the ports b and c, the reference liquid 30 in the reference liquid tank 24 is moved to the line L31, the measuring path A4 of the measuring valve M4, the line L32, and the switching valves V8 (b, c ), It is fed through the line L33, and the pump P5 is driven for 1 minute and then stopped.
[0042]
Next, the switching valve V6 is switched to ports a and b, the metering valve M2 is switched by the rotation of the rotor R2, the metering path A2 is connected to the lines L21 and L22, and the reagent solution 29 in the metering path A2 is the carrier liquid after the line L22. Inject into the channel. After several tens of seconds, the metering valve M4 is switched to connect the metering path A4 to the lines L23 and L24, and the reference liquid 30 in the metering path A4 is injected into the carrier liquid channel after the line L24. At this time, the luminescent reagent reacts with hydrogen peroxide as the chemiluminescent active species to emit light, so the detector 21 detects the light emission amount. A detection signal is sent to the control device 27, and the concentration of the reference solution 30 is determined from the amount of light emitted. The drained liquid after the measurement is discharged from the line L33.
[0043]
Thereafter, the switching valve V8 is switched to ports a and b, the metering valve M4 is switched to connect the metering path A4 to the lines L31 and L32, and the pump P5 is driven to send the reference liquid 30. As a result, the carrier liquid 28 in the metering path A4 is discharged from the line L32, the switching valves V8 (a, b) and the line L35 to the drain tank 25, and the reference liquid 30 is injected into the metering path A4. After a few minutes, the switching valve V8 is switched to the ports b and c, and the pump P5 is stopped.
[0044]
Similarly, the switching valve V7 is switched to ports a and b, the metering valve M2 is switched to connect the metering path A2 to the lines L27 and L28, and the pump P4 is driven to send the reagent solution 29. As a result, the carrier liquid 28 in the measuring channel A2 is discharged to the drainage tank 25 through the line L28, the switching valve V7 (a, b) and the line L34, and the reagent solution 29 is injected into the measuring channel A2. After a few minutes, the switching valve V7 is switched to the ports b and c, and the pump P4 is stopped. Then, the metering valve M2 is switched to connect the metering path A2 to the lines L21 and L22, and the reagent solution 29 is injected into the carrier liquid channel after the line L22.
[0045]
On the other hand, the diluted sample sent from the sampling device 10 through the line L13 passes through the measuring path A3 of the measuring valve M3 and enters the line L36. When the diluted sample passes the sensor 32, the signal passes through the measuring path A3 of the measuring valve M3. Switch to the line L22, L23 side and stop the pump P2. As a result, the diluted samples in the lines L13 and L36 are held as they are.
[0046]
By switching the metering valve M3, the diluted sample in the metering channel A3 is injected into the carrier liquid flow path after the line L23, and the already-injected reagent solution 29 reacts with hydrogen peroxide as the luminescent active species of the diluted sample. Emits light. The amount of emitted light is detected by the detector 21, and the detection result is sent to the control device 27. The control device 27 calculates the concentration of the chemiluminescent active species in the sample from the relational expression between the light emission amount of the reference solution 30 already detected and the light emission amount of the diluted sample, and records and outputs it.
[0047]
Thereafter, the metering valve M3 is switched to connect the metering path A3 to the lines L13 and L36, the pump P2 is driven, the carrier liquid 18 is sent to clean the line, and the drainage is discharged to the drainage tank 25. After a few minutes, the pump P2 is stopped and the switching valve V4 is switched to the ports a and b, so that the line L14, the switching valve V4 (a, b), the line L12, the switching valve V1 (a, b), the line L7, sampling Gas flows through the valve 11, the line L6, the switching valve V3 (b, c), the line L13, the metering valve M3 (A3), and the line L36, and the system is dried.
[0048]
By repeating the above operation, it is possible to automatically analyze the peroxide as the chemiluminescent active species in the sample.
[0049]
The apparatus of FIG. 1 can also be provided with a base solution tank for storing a base solution composed of a reverse micelle solution containing a base in the inner aqueous phase of the reverse micelle, and a fifth metering valve for measuring the base solution. In this case, the measurement accuracy of the reference solution and the diluted sample can be further improved by allowing the base to be adsorbed to the flow cell by passing the detector 21 once before causing the reference solution 30 to emit light.
[Brief description of the drawings]
FIG. 1 is a flowchart of a peroxide analyzer according to an embodiment.
FIG. 2 is a schematic diagram showing the structure of a reverse micelle.
FIG. 3 is a schematic diagram showing a chemiluminescence reaction occurring in reverse micelles.
FIG. 4 is a schematic diagram showing the principle of chemiluminescence generated in reverse micelles.
[Explanation of symbols]
1 Reverse micelle
2 Surfactant
2a Hydrophilic group
2b Hydrophobic group
3 Internal water phase
4 Bulk solvent
10 Sampling equipment
11 Sampling valve
11a stem
11b Dilution chamber
13 Diluent tank
14 Transport liquid tank
15 processes
16 Test object
17 Diluent
18 Transport liquid
20 Measuring device
21 Detector
22 Carrier liquid tank
23 Reagent solution tank
24 reference tank
25 Drainage tank
27 Control device
28 Carrier liquid
29 Reagent solution
30 standard solution
31 Drainage
32 sensors
M1, M2, ... Metering valve

Claims (9)

A method in which a reagent solution containing reverse micelles of a luminescent reagent is reacted with a peroxide contained in an organic solvent, and the peroxide is analyzed by a reverse micelle media chemiluminescence method,
In the sampling device, a certain amount of sample is collected from the process by the sampling valve, diluted with the diluent measured by the first metering valve to prepare a diluted sample, and the second and third metering valves and the detector in the measuring device. The carrier solution is fed through, the reagent solution weighed by the second metering valve is injected into the carrier fluid channel, and the diluted sample prepared by the sampling device is metered by the third metering valve and injected into the carrier fluid channel. A peroxide analysis method in which the amount of luminescence is detected by a detector after reacting with reagent solution. The method according to claim 1, wherein the diluted sample prepared in the sampling device is sent to the measuring device by a carrier liquid. In the measuring apparatus, the carrier liquid is sent through the second to third metering valves and the detector, the reagent solution weighed by the first metering valve is injected into the carrier liquid channel, and the reference liquid weighed by the fourth metering valve is used. 3. The peroxide concentration of the sample is calculated from a relational expression between the amount of light emitted from the reference liquid and the amount of light emitted from the sample after being injected into the carrier liquid flow path and detected by a detector. the method of. An apparatus for analyzing a peroxide by reverse micelle media chemiluminescence method by reacting a reagent solution containing a reverse micelle of a luminescent reagent with a peroxide contained in an organic solvent,
A sampling device for taking a fixed amount of sample from the process by the sampling valve and diluting with a diluent measured by the first metering valve to prepare a diluted sample;
The carrier liquid flow path is formed through the bypass path of the second and third metering valves having the metering path and the bypass path and the detector, and the reagent solution measured in the metering path of the second metering valve is injected into the carrier liquid flow path. And a measuring device that measures the diluted sample prepared by the sampling device through the measuring channel of the third measuring valve, injects it into the carrier liquid channel, reacts with the reagent solution, and detects the amount of luminescence with the detector. Oxide analyzer. 5. The method according to claim 4, wherein the sampling device has means for sending the prepared diluted sample to the measuring device with a carrier liquid. The measuring device sends the carrier liquid through the bypass path and the detector of the second to fourth metering valves, injects the reagent solution metered in the metering path of the first metering valve into the carrier liquid channel, and the fourth metering. It is configured to inject the reference liquid measured in the valve measurement path into the carrier liquid flow path and detect the light emission amount of the reference liquid with a detector.
6. The apparatus according to claim 4, further comprising a control device that calculates a peroxide concentration of the sample from a relational expression between the light emission amount of the reference solution and the light emission amount of the sample. 5. The sampling valve has a system for collecting a fixed amount of sample from the process, and a dilution chamber for introducing the mixed sample and the diluent measured by the first metering valve to prepare a diluted sample. The apparatus in any one of thru | or 6. 8. The apparatus according to claim 7, wherein the sampling device has means for introducing and stirring the gas into the dilution chamber. The apparatus according to claim 6, wherein the sampling device has means for introducing a gas into a path for sending the prepared diluted sample to the measuring device with a carrier liquid and discharging the liquid in the system.

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