CN112304881A - Analysis device, program, and analysis method - Google Patents
Analysis device, program, and analysis method Download PDFInfo
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- CN112304881A CN112304881A CN202010739317.2A CN202010739317A CN112304881A CN 112304881 A CN112304881 A CN 112304881A CN 202010739317 A CN202010739317 A CN 202010739317A CN 112304881 A CN112304881 A CN 112304881A
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- 238000004458 analytical method Methods 0.000 title claims abstract description 52
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 227
- 239000007788 liquid Substances 0.000 claims abstract description 207
- 238000002835 absorbance Methods 0.000 claims abstract description 145
- 239000012490 blank solution Substances 0.000 claims abstract description 123
- 239000000243 solution Substances 0.000 claims abstract description 111
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 88
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 76
- 239000012488 sample solution Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000523 sample Substances 0.000 claims description 111
- 238000006243 chemical reaction Methods 0.000 claims description 100
- 238000001514 detection method Methods 0.000 claims description 90
- 238000000197 pyrolysis Methods 0.000 claims description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 47
- 229910052698 phosphorus Inorganic materials 0.000 claims description 47
- 239000011574 phosphorus Substances 0.000 claims description 47
- 238000003303 reheating Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000002211 L-ascorbic acid Substances 0.000 claims description 6
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005259 measurement Methods 0.000 abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 99
- 229910052757 nitrogen Inorganic materials 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 238000011144 upstream manufacturing Methods 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000011481 absorbance measurement Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000011088 calibration curve Methods 0.000 description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- MNPICTSLNPAQOZ-UHFFFAOYSA-K copper;sodium;phosphate Chemical compound [Na+].[Cu+2].[O-]P([O-])([O-])=O MNPICTSLNPAQOZ-UHFFFAOYSA-K 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B15/00—Systems controlled by a computer
- G05B15/02—Systems controlled by a computer electric
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N2021/786—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour with auxiliary heating for reaction
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pathology (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Automation & Control Theory (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention provides an analytical device based on an absorbance analysis method, which can perform accurate measurement even if the ambient temperature is low, and a program and an analytical method for controlling the analytical device. A method for analyzing a sample solution, wherein a heated decomposition solution obtained by subjecting a sample solution to thermal decomposition or a liquid obtained by adding a predetermined reagent to the heated decomposition solution is used as a blank solution, a color developing reagent is reacted with the blank solution after the absorbance of the blank solution is measured to obtain a color developing solution, the absorbance of the obtained color developing solution is measured, and the blank solution is reheated after the absorbance of the blank solution is measured and before the color developing reagent is reacted with the blank solution.
Description
Technical Field
The present invention relates to an analysis device, a program, and an analysis method. More specifically, the present invention relates to an analyzer for measuring absorbance by decomposing a sample liquid by heating and then reacting a reagent for color development with the decomposed sample liquid, and a program and an analysis method for controlling the analyzer.
Background
In order to measure the concentration of total phosphorus, total chromium, total copper, total nickel, total manganese, and the like contained in a sample solution, an analyzer by an absorbance analysis method in which a color developing reagent is added after the sample solution is decomposed by heating is generally used.
In the above-described analyzer, in order to perform blank correction, blank correction is performed using a liquid before addition of a color developing reagent as a blank solution (non-patent documents 1 and 2).
Documents of the prior art
Non-patent documents:
non-patent document 1: automatic measuring apparatus for Total Nitrogen and Total phosphorus/COD model NPW-160, DKK, Toya DKK, 2016, 7.7.7.7.7.251-252
Non-patent document 2: automatic heavy Metal measurement device Using instruction manual HMA-TCR model, HMA-CR6 model, HMA-TCU model, HMA-TNI model, HMA-TMN model, Doyaya DKK corporation, 11/10/2015, P141-145
Disclosure of Invention
Problems to be solved by the invention
In the analyzers based on the absorbance analysis methods disclosed in non-patent documents 1 and 2, when the ambient temperature is low and the amount of liquid in the sample liquid is small, the concentration of the detected measurement target component may be lower than the actual concentration.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an analyzer based on an absorbance analysis method, a program for controlling the analyzer, and an analysis method, which can perform accurate measurement even when the ambient temperature is low and the amount of liquid of a sample liquid is small.
Means for solving the problems
To achieve the above object, the present invention adopts the following structure.
The 1 st aspect of the present invention is an analysis device including: a thermal decomposition unit; a reaction tank in which a liquid is movable between the reaction tank and the pyrolysis section; an absorbance detecting section for allowing a liquid to move between the absorbance detecting section and the reaction tank; and a control unit for sequentially executing the following steps under the control of the control unit:
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: transporting the thermal decomposition liquid or a liquid obtained by adding a predetermined reagent to the thermal decomposition liquid, as a blank solution, from the reaction tank to the absorbance detection unit;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting a color-developing reagent with the blank solution in the reaction tank to obtain a color-developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: the absorbance of the color-developing solution is measured by the absorbance detection unit.
In the 2 nd aspect of the present invention, in the analyzer according to the 1 st aspect, the step 1 is performed after a sample liquid and a pyrolysis reagent are introduced into the reaction tank and are transported from the reaction tank to the pyrolysis section.
The 3 rd aspect of the present invention is an analysis device including: a thermal decomposition unit; a reaction tank in which a liquid is transferred between the reaction tank and the pyrolysis unit; an absorbance detection unit for transferring a liquid between the reaction tank and the liquid transport unit; and a control unit for sequentially executing the following steps under the control of the control unit:
the preparation method comprises the following steps: introducing a sample solution and a potassium peroxodisulfate solution into the reaction tank, and transporting them from the reaction tank to the thermal decomposition unit;
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: a step of transferring a liquid obtained by adding an L-ascorbic acid solution to the heated decomposition liquid from the reaction tank to the absorbance detection unit as a blank solution;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting an ammonium molybdate solution with the blank solution in the reaction tank to obtain a color developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: measuring the absorbance of the color developing solution in the absorbance detection unit;
step 11: and (4) determining the total phosphorus concentration of the sample solution according to the difference between the absorbance of the color developing solution obtained in the step (10) and the absorbance of the blank solution obtained in the step (4).
The 4 th aspect of the present invention is a program for causing a control unit of an analysis device including a pyrolysis unit, a reaction tank in which a liquid is movable between the pyrolysis unit and the reaction tank, an absorbance detection unit in which a liquid is movable between the reaction tank and the reaction tank, and a control unit to execute processing including:
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: transporting the thermal decomposition liquid or a liquid obtained by adding a predetermined reagent to the thermal decomposition liquid, as a blank solution, from the reaction tank to the absorbance detection unit;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting a color-developing reagent with the blank solution in the reaction tank to obtain a color-developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: the absorbance of the color-developing solution is measured by the absorbance detection unit.
The 5 th aspect of the present invention is a method for analyzing a sample solution, in which a heated decomposition liquid obtained by subjecting a sample solution to thermal decomposition or a liquid obtained by adding a predetermined reagent to the heated decomposition liquid is used as a blank solution, a color developing reagent is reacted with the blank solution after measuring the absorbance of the blank solution to obtain a color developing solution, and the absorbance of the obtained color developing solution is measured, wherein the blank solution is heated again after measuring the absorbance of the blank solution and before reacting the color developing reagent with the blank solution.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the analyzer, the program for controlling the analyzer, and the analyzing method of the present invention, even when the ambient temperature is low, the measurement by the absorbance analysis method can be accurately performed.
Drawings
Fig. 1 is a schematic configuration diagram of an analysis device according to 1 embodiment of the present invention.
FIG. 2 is a flow chart of an analysis method according to 1 embodiment of the present invention.
FIG. 3 is a flow chart of an analysis method according to another embodiment of the present invention.
FIG. 4 is a flow chart of an analysis method according to another embodiment of the present invention.
FIG. 5 is a flow chart of an analysis method according to another embodiment of the present invention.
FIG. 6 is a flow chart of an analysis method according to another embodiment of the present invention.
Description of the reference numerals
10: reaction tank
11: sample cup
12: cover member
13: heating tank
15: buffer box
20: absorbance detecting section
30: control unit
L1: detection tubing
L2: sample liquid piping
L3: no. 1 reagent discharge piping
L4: no. 2 reagent discharge piping
L5: 3 rd reagent discharge piping
L6: decomposition piping for total nitrogen
L7: decomposition piping for total phosphorus
L8: pure water pipe
L9: liquid discharge piping
L10: pipe for pressurization
L12: shared piping
L13: total nitrogen decomposition liquid discharge pipe
P1: pump for detection
P2: sample liquid pump
P3: 1 st reagent pump
P4: 2 nd reagent pump
P5: 3 rd reagent pump
P6: 4 th reagent pump
P7: 5 th reagent pump
P8: pure water pump
P9: liquid discharge pump
P10: air pump
Detailed Description
< analytical method >
The analysis method of the present invention is suitable for the following sample liquid analysis methods: a heated decomposition liquid obtained by heating and decomposing a sample liquid or a liquid obtained by adding a predetermined reagent to the heated decomposition liquid is used as a blank solution, the absorbance of the blank solution is measured, then a color developing reagent is reacted with the blank solution to obtain a color developing solution, and the absorbance of the obtained color developing solution is measured.
In the present invention, the color-developing reagent is a reagent to which the color-developing solution to be measured for absorbance is obtained by adding the reagent. The color-developing reagent may be a single compound or a combination of a plurality of compounds.
The present inventors have studied the reason why the concentration of the measurement target component detected when the ambient temperature is low and the amount of the sample liquid is small is lower than the actual concentration, and as a result, they have found that the reason is: the temperature of the blank solution decreases during the measurement of absorbance, and the reaction with the color-developing reagent does not proceed sufficiently.
That is, the reason for this was found to be: the thermally decomposed solution obtained by thermally decomposing the sample solution is usually used as a blank solution after it is left to cool to a temperature at which absorbance measurement can be performed, and when the ambient temperature is low and the amount of the sample solution is small, the temperature of the blank solution after absorbance measurement is lowered to a temperature lower than a temperature necessary for sufficient reaction with the color-developing reagent.
Therefore, in the analysis method of the present invention, after the absorbance of the blank solution is measured, and before the color-developing reagent is reacted with the blank solution, the blank solution is heated again.
The smaller the amount of the blank solution, the more preferable the present invention is applicable. This is because the smaller the amount of the blank solution, the more easily the temperature is decreased in a short time. Recent analyzers reduce the consumption of reagents to the limit from the viewpoints of resource saving and environmental protection. Therefore, the amount of the liquid to be measured such as a blank solution in the sample cup becomes extremely small, and the present invention can be preferably applied.
Specifically, the present invention is preferably applied to a case where the liquid amount of the blank solution is 10mL or less, and more preferably to a case where the liquid amount of the blank solution is 5mL or less.
Further, the present invention can be preferably applied to an analysis method in which absorbance measurement and thermal decomposition are performed at different sites, respectively, and a liquid is moved between the two sites.
In addition, the present invention is particularly preferably applicable to an analysis method in which absorbance measurement, thermal decomposition, and reagent addition are performed at different places, respectively, and a liquid passes through a place where the reagent is added when moving between the places where the absorbance measurement and the thermal decomposition are performed.
This is because the longer the time for moving the blank solution such as the heated decomposition liquid, the more likely the temperature of the blank solution or the like is to be lowered.
The heating temperature and the heating time in reheating are not particularly limited as long as the temperature at which the reaction with the color-developing reagent is easily performed can be set.
For example, in 1974, the environmental hall (current environmental province) announced "total phosphorus measurement by the 120 ℃ potassium peroxodisulfate decomposition method — molybdenum blue absorptiometry" No. 64 "detection method according to the drainage standard determined by the environmental minister and stipulated by the ministry of ministry to determine drainage standards", JIS K0102: 201646.3 and the Chinese Standard HJ/T103-2003 and GB 11893-89, ammonium molybdate solution reacts with phosphate ions in the heated decomposition liquid in the presence of L-ascorbic acid solution.
The present inventors confirmed that the reaction was completed within 5 minutes at a temperature of 15 ℃ or higher, but color development was not completed even after 15 minutes at a temperature lower than that.
Therefore, when the ambient temperature is low and the reaction is carried out in an environment where the temperature of the blank solution may fall below 15 ℃, reheating is preferably carried out so that the temperature of the blank solution becomes 15 ℃ or higher.
When another measurement target component is analyzed, it is also preferable to appropriately reheat to an appropriate temperature depending on the type of reaction and the type of the color-developing reagent used.
Although the method of reheating is not particularly limited, when the place where the absorbance measurement is performed is different from the place where the thermal decomposition is performed, it is preferable to return the blank solution to the place where the thermal decomposition is performed and reheat it.
When the apparatus is provided with a pyrolysis section heated in a heating tank, normally, even in a standby state other than the time of pyrolysis, the heating tank is kept weakly heated and a preheating temperature of about 70 ℃. Therefore, for example, when the amount of the blank solution is 5mL or less, the temperature can be easily 15 ℃ or more by returning the blank solution to the thermal decomposition part for 10 to 60 seconds.
In addition, even if the heating decomposition unit is not continuously heated during standby, the waste heat can be used by returning the blank solution to the heating decomposition unit.
When the place where the absorbance measurement is performed is the same as the place where the thermal decomposition is performed, for example, when the reaction tank to which the reagent is added can be heated and an optical system for measuring the absorbance in the reaction tank is provided, the reaction tank may be heated again as it is.
The absorbance of the blank solution and the absorbance of the developing solution obtained by the analysis method of the present invention can be used to determine the concentration of the measurement target component in the sample solution.
In general, the concentration of the measurement target component in the sample liquid is calculated by subtracting the absorbance of the blank solution from the absorbance of the developing solution based on the previously obtained calibration curve information.
The analysis method of the present invention may further include a step of subtracting the absorbance of the blank solution from the absorbance of the developing solution.
The method may further include a step of converting a value obtained by subtracting the absorbance of the blank solution from the absorbance of the color developing solution into the concentration of the component to be measured.
< analytical device >
Fig. 1 shows a total nitrogen and total phosphorus analyzer as an analyzer according to an embodiment of the present invention, but the analyzer according to the present invention is not limited to this embodiment, and its specific configuration and operation procedure may be variously modified.
The analysis device of the present embodiment includes: a reaction tank 10, a heating tank 13, an absorbance detection unit 20, piping and pumps for moving the liquid, and a control unit 30 for controlling the entire apparatus.
The reaction vessel 10 is composed of a sample cup 11 and a lid member 12 covering the sample cup 11, and a detection pipe L1, a sample liquid pipe L2, a 1 st reagent discharge pipe L3, a2 nd reagent discharge pipe L4, a 3 rd reagent discharge pipe L5, a total nitrogen decomposition pipe L6, a total nitrogen decomposition liquid discharge pipe L13, a total phosphorus decomposition pipe L7, a deionized water pipe L8, and a liquid discharge pipe L9 penetrate the lid member 12 and are inserted into the reaction vessel 10.
The upstream end of the detection pipe L1 is inserted into the sample cup 11, and the downstream end is inserted into the waste liquid tank T7. Further, the detection pipe L1 includes an absorbance detection unit 20, a buffer tank 15, and a detection pump P1 provided in this order from the upstream side.
That is, the sample cup 11 of the reaction vessel 10 and the absorbance detection unit 20 are connected by the detection pipe L1, and the liquid can be moved by the detection pump P1.
The absorbance detection unit 20 is an absorptiometer having a flow cell.
Fig. 1 shows only the flow cell portion, but the absorbance detection unit 20 includes: a light source for irradiating the flow cell with light, a light detection unit for detecting light transmitted through the flow cell, and an optical member such as a lens provided between the light source and the light detection unit.
The buffer tank 15 is connected to the downstream side of the flow cell of the absorbance detection unit 20 in the middle of the detection pipe L1. The buffer tank 15 is configured to: the upstream side is located above (higher than) the downstream side.
The buffer tank 15 has a portion formed such that the inner diameter gradually increases and then gradually decreases from upstream to downstream. That is, it is formed to gradually increase and then gradually decrease from downstream to upstream even when viewed from downstream.
By having a portion gradually increasing from the downstream to the upstream, when a small amount of liquid flows back from the downstream, the area of the small amount of liquid in the liquid film shape increases as it rises, and thus the liquid film breaks in the middle. Therefore, the liquid retaining film that flows backward can be prevented from reaching the flow cell side.
Further, since the detection pipe has a portion gradually increasing from the downstream to the upstream and then gradually decreasing, the detection pipe can be connected to the middle of the detection pipe L1.
The detection pump P1 is a pump that can feed the liquid in the detection pipe L1 in either the forward direction from upstream to downstream or the reverse direction from downstream to upstream.
The detection pump P1 of the present embodiment is a peristaltic pump. Peristaltic pumps are also known as hose pumps or roller pumps, in which a flexible tube is squeezed by rollers to deliver liquid or gas. By reversing the direction in which the roller presses the flexible tube, the direction of liquid or air supply can be reversed. As a commercially available product of the peristaltic pump, a PERISTA pump (registered trademark) can be used.
As a pump provided in the detection pipe L1 of the present invention, a syringe pump provided with a flow path switching device such as a three-way valve on the discharge port side can be used.
The sample liquid pipe L2 has an upstream end connected to a sample liquid supply source such as a reservoir, not shown, and a downstream end disposed at a position where the sample liquid can be discharged into the sample cup 11. A sample liquid pump P2 is provided in the middle of the sample liquid pipe L2.
The 1 st, 2 nd and 3 rd reagent discharge pipes L3, L4, and L5 are all reagent discharge pipes, and their downstream ends are disposed at positions where the liquid reagents can be discharged into the respective sample cups 11.
On the other hand, a pressurizing pipe L10 is connected to the upstream end of each reagent discharge pipe, and an air pump P10 is provided in the pressurizing pipe L10. The air pump P10 is configured so that the pressurization pipe L10 is not closed when stopped, and the upstream end of the pressurization pipe L10 is open to the atmosphere.
The 5 th normally-closed valve V5 is provided on the 1 st reagent discharge pipe L3 on the upstream side connected to the pressurizing pipe L10, and the pipe a, the pipe B, and the pipe C are connected in this order from the upstream side on the downstream side of the 1 st reagent discharge pipe L3.
The 6 th normally-closed valve V6 is provided on the upstream side of the 2 nd reagent discharge pipe L4 connected to the pressurizing pipe L10, and the pipe D is connected to the downstream side of the 2 nd reagent discharge pipe L4.
The 7 th normally-closed valve V7 is provided on the upstream side of the 3 rd reagent discharge pipe L5 connected to the pressurizing pipe L10, and the pipe E is connected to the downstream side of the 3 rd reagent discharge pipe L5.
The upstream end of the pipe a is inserted into the 1 st reagent tank T1 containing the sodium hydroxide solution, the downstream end thereof is connected to the 1 st reagent discharge pipe L3 at the connection point a, and the 1 st reagent pump P3 is provided in the middle thereof.
The upstream end of the pipe B is inserted into the 2 nd reagent tank T2 containing potassium peroxodisulfate solution, the downstream end thereof is connected to the 1 st reagent discharge pipe L3 at the connection point B, and the 2 nd reagent pump P4 is provided in the middle thereof.
The pipe C has an upstream end inserted into a 3 rd reagent tank T3 containing an L-ascorbic acid solution, a downstream end connected to a 1 st reagent discharge pipe L3 at a connection point C, and a 3 rd reagent pump P5 provided in the middle.
The pipe D has an upstream end inserted into a 4 th reagent tank T4 containing a hydrochloric acid solution, a downstream end connected to a2 nd reagent discharge pipe L4 at a connection point D, and a 4 th reagent pump P6 provided in the middle.
The pipe E has an upstream end inserted into a 5 th reagent tank T5 containing an ammonium molybdate solution, a downstream end connected to a 3 rd reagent discharge pipe L5 at a connection point E, and a 5 th reagent pump P7 provided in the middle.
The pipe a, the pipe B, the pipe C, the pipe D, and the pipe E are all reagent supply pipes that supply a liquid reagent to the reagent discharge pipe, and the reagent pump provided in each of the reagent supply pipes is a liquid feeding unit that moves the liquid reagent.
By operating the 1 st reagent pump P3, the reagent in the 1 st reagent tank T1 is supplied to the connected reagent discharge pipe; by operating the 2 nd reagent pump P4, the reagent in the 2 nd reagent tank T2 is supplied to the connected reagent discharge pipe; by operating the 3 rd reagent pump P5, the reagent in the 3 rd reagent tank T3 is supplied to the connected reagent discharge pipe; by operating the 4 th reagent pump P6, the reagent in the 4 th reagent tank T4 is supplied to the connected reagent discharge pipe; by operating the 5 th reagent pump P7, the reagent in the 5 th reagent tank T5 is supplied to the connected reagent discharge pipe.
The reagent pumps provided in the respective reagent supply pipes close the reagent supply pipes while keeping the reagent pumps airtight at the positions where the reagent pumps are provided when the reagent pumps are stopped. Thus, the reagent can be held between the pump and the connection point between the reagent supply pipe and the reagent discharge pipe provided with each reagent pump at the time of stopping.
As the reagent pump provided in the reagent supply pipe, a syringe pump or a peristaltic pump having a check valve can be preferably used.
In the present embodiment, in the standby state, the liquid reagent in each reagent supply pipe is filled from the upstream end of the reagent supply pipe to each connection point, and all the reagents supplied from any one of the reagent supply pipes to any one of the reagent discharge pipes across the connection points are discharged into the cuvette 11 of the reaction vessel 10.
In the present specification, "discharge all" means discharge substantially all, and corresponds to "discharge all" when a small amount of residual liquid inevitably adheres to and remains in the piping.
In the 1 st aspect, the reagent pump provided in any one of the reagent supply pipes connected to the 5 th, 6 th, and 7 th normally-closed valves V5, V6, and V7 is operated in a state where the air pump P10 is operated and any one of the valves is Opened (ON). Then, all the reagent that has passed from the reagent supply pipe to the reagent discharge pipe beyond the connection point can be discharged to the cuvette 11.
For example, when the 1 st reagent pump P3 is operated in a state where the 5 th normally-closed valve V5 is Opened (ON) and the air pump P10 is operated, all of the portion of the reagent in the 1 st reagent tank T1 that reaches the 1 st reagent discharge pipe L3 from the pipe a beyond the connection point a is immediately discharged to the cuvette 11 by air.
In the 2 nd aspect, the height position of the connection point is set higher than the height position of the downstream end of each reagent discharge pipe.
Then, when the reagent pump connected to any one of the reagent supply pipes is operated in a state where the 5 th, 6 th, and 7 th normally-closed valves V5, V6, and V7 are all closed (OFF) and the air pump P10 is closed, a predetermined amount of the liquid reagent moves to the connection point of the reagent discharge pipe. The liquid reagent that has reached the reagent discharge pipe beyond the connection point enters the downstream side of the reagent discharge pipe because the upstream side is closed by the normally closed valve.
Thereafter, when the reagent pump is stopped and the normally-closed valve provided in the reagent discharge pipe into which the liquid reagent has been introduced is Opened (ON), the connection point is connected to the upstream end of the pressurization pipe L10 in a state in which the connection point is open to the atmosphere, and therefore all of the liquid reagent supplied to the reagent discharge pipe beyond the connection point falls by its own weight and is discharged from the downstream end of the reagent discharge pipe into the sample cup 11.
When there is a portion higher than the connection point between the connection point and the downstream end, the reagent pump needs to be stopped after the liquid reagent is introduced to a portion lower than the connection point (gravity drop point) beyond the higher portion. If the liquid is not filled up to the self-weight falling point, the liquid does not fall down by its self-weight even if the connection point is opened to the atmosphere.
Then, when the air pump P10 is operated without changing the open state of the Opened (ON) valve, a small amount of residual liquid remaining downstream of each connection point of the reagent discharge pipe can be discharged into the cuvette 11.
For example, the reagent in the 1 st reagent tank T1 is supplied into the sample cup 11 as described below. First, in a state where the 5 th, 6 th, and 7 th normally-closed valves V5, V6, and V7 are all closed (OFF) and the air pump P10 is closed, the 1 st reagent pump P3 is operated to move a predetermined amount of the reagent in the 1 st reagent tank T1 from the pipe a to the connection point a. The reagent that has reached the 1 st reagent discharge pipe L3 beyond the connection point a enters the 1 st reagent discharge pipe L3 downstream because the upstream side is closed by the 5 th normally-closed valve V5.
Thereafter, when the reagent pump is stopped and the normally-closed valve provided in the reagent discharge pipe into which the liquid reagent is introduced is Opened (ON), the connection point a is connected to the upstream end of the pressurization pipe L10 in the state of being opened to the atmosphere, and therefore, all the liquid reagent supplied to the 1 st reagent discharge pipe L3 beyond the connection point a falls by its own weight and is discharged from the downstream end of the 1 st reagent discharge pipe L3 into the sample cup 11.
Then, when the air pump P10 is operated while the 5 th normally-closed valve V5 is kept Open (ON), a small amount of residual liquid remaining ON the downstream side of the connection point a can be discharged into the sample cup 11.
In either case, the entire amount of the reagent that reaches the reagent discharge pipe from the reagent supply pipe across the connection point can be introduced into the cuvette 11. Further, since the liquid in the sample cup 11 can be stirred by air, the introduced reagent and the sample liquid can be sufficiently mixed.
Further, after the reagent is introduced into the cuvette 11, the reagent is held in a state filled between the connection point of each reagent supply pipe and the reagent pump, and therefore, the reagent can be supplied for the next reagent supply.
Further, since the reagent does not enter the reagent discharge pipe after the reagent is introduced into the cuvette 11, the reagent can be prevented from accidentally dropping from the tip of the reagent discharge pipe into the cuvette 11, and a plurality of reagent supply pipes can be connected to one reagent discharge pipe.
The total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 each have a pyrolysis unit above the reaction tank 10. The thermal decomposition unit is a portion where the total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 are covered by the heating tank 13.
The downstream ends of the total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 are inserted into the bottom of the sample cup 11.
That is, the total nitrogen-measuring pyrolysis unit is connected to the sample cup 11 of the reaction vessel 10 via the total nitrogen decomposition pipe L6, and the total phosphorus-measuring pyrolysis unit is connected to the sample cup 11 of the reaction vessel 10 via the total phosphorus decomposition pipe L7, and as described below, the liquid can be moved between each pyrolysis unit and the sample cup 11 by the action of a pump or a valve.
A 1 st normally closed valve V1 is provided on the side of the thermal decomposition unit of the total nitrogen decomposition pipe L6 closer to the reaction tank 10, and a2 nd normally closed valve V2 is provided on the opposite side of the reaction tank 10.
Similarly, a 3 rd normally closed valve V3 is provided on the side of the thermal decomposition unit of the total phosphorus decomposition pipe L7 closer to the reaction tank 10, and a 4 th normally closed valve V4 is provided on the side opposite to the reaction tank 10.
Further, an upstream end side of the total nitrogen decomposition liquid discharge pipe L13 is connected between the pyrolysis unit of the total nitrogen decomposition pipe L6 and the 1 st normally-closed valve V1, and the 9 th normally-closed valve V11 is provided in the total nitrogen decomposition liquid discharge pipe L13.
The upstream ends of the total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 are connected to the pressurization pipe L10 via the common pipe L12.
An 8 th normally-closed valve V8 is provided between a portion of the pressurization pipe L10 to which the common pipe L12 is connected and portions to which the 1 st reagent discharge pipe L3, the 2 nd reagent discharge pipe L4, and the 3 rd reagent discharge pipe L5 are connected.
The deionized water pipe L8 has an upstream end inserted into the deionized water tank T8 and a downstream end disposed at a position where deionized water can be discharged into the sample cup 11.
The pure water pipe L8 is provided with a 1 st three-way valve V9 and a2 nd three-way valve V10 in this order from the upstream side.
The 1 st three-way valve V9 is connected to a discharge port of a pure water pump P8. In the present embodiment, the pure water pump P8 is a syringe pump.
In the 1 st three-way valve V9, the plain water pump P8 is a common port on the discharge port side, the plain water tank T8 is a normally closed port, and the 2 nd three-way valve V10 is a normally open port.
Further, the 2 nd three-way valve V10 is connected to the upstream end of the heating bath cleaning pipe L11. The downstream end of the heating tank cleaning pipe L11 is connected to the connection point between the pressurizing pipe L10 and the common pipe L12.
In the 2 nd three-way valve V10, the 1 st three-way valve V9 side is a common port, the downstream end side of the deionized water pipe L8 is a normally closed port, and the heating bath cleaning pipe L11 side is a normally open port.
The liquid in the sample cup 11 is sucked up to the thermal decomposition unit by the suction operation of the pure water pump P8. The timing of the updraft to the respective thermal decomposition units of the total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 is different.
Before the start of the suction operation of the pure water pump P8 for sucking up the liquid to the pyrolysis unit, the plunger of the pure water pump P8 is positioned at the discharge position.
The suction operation of the deionized water pump P8 when sucking the liquid into the total nitrogen decomposition pipe L6 is performed in a state where the 1 st and 2 nd normally-closed valves V1 and V2 are Opened (ON), the 3 rd and 4 th normally-closed valves V3 and V4 and the 9 th normally-closed valve V11 are closed (OFF), the 8 th normally-closed valve V8 is closed (OFF), the 1 st three-way valve V9 is closed (the T8 side is closed), and the 2 nd three-way valve V10 is closed (the L11 side is opened).
The suction operation of the deionized water pump P8 when sucking the liquid into the total phosphorus decomposition pipe L7 is performed in a state where the 1 st and 2 nd normally closed valves V1 and V2 and V11 are closed (OFF), the 3 rd and 4 th normally closed valves V3 and V4 are Opened (ON), the 8 th normally closed valve V8 is closed (OFF), the 1 st three-way valve V9 is closed (the T8 side is closed), and the 2 nd three-way valve V10 is closed (the L11 side is open).
The heated decomposition portion into which the liquid is introduced is pressurized by feeding air under pressure. By operating the air pump P10, air is pumped to the pyrolysis unit.
When the pyrolysis portion of the total nitrogen decomposition pipe L6 is pressurized, the 1 st normally-closed valve V1, the 9 th normally-closed valve V11, the 3 rd normally-closed valve V3, and the 4 th normally-closed valve V4 are closed (OFF), the 2 nd normally-closed valve V2 is Opened (ON), the 8 th normally-closed valve V8 is Opened (ON), and the 2 nd three-way valve V10 is opened (the V8 side is closed).
When the pyrolysis section of the total phosphorus decomposition pipe L7 is pressurized, the 1 st normally-closed valve V1, the 2 nd normally-closed valve V2, the 9 th normally-closed valve V11, and the 3 rd normally-closed valve V3 are closed (OFF), the 4 th normally-closed valve V4 is Opened (ON), the 8 th normally-closed valve V8 is Opened (ON), and the 2 nd three-way valve V10 is opened (the V8 side is closed).
Then, in a state where the air pump P10 is stopped and all of the 1 st to 4 th normally-closed valves V1 to V4 and the 1 st three-way valve V9 are closed (OFF), the pyrolysis unit is heated by the heater tank 13, and the liquid introduced into each pyrolysis unit is pyrolyzed.
The temperature of the heating tank 13 was preheated to about 70 ℃ in all steps except the time of thermal decomposition, and was 120 ℃ in the time of thermal decomposition.
Thereafter, the timing of releasing the pressure of the pyrolysis portion of each of the total nitrogen decomposition pipe L6 and the total phosphorus decomposition pipe L7 and returning the liquid (pyrolysis liquid) to the sample cup 11 was different.
By Opening (ON) the 9 th normally-closed valve V11, the pyrolysis portion of the total nitrogen decomposition pipe L6 is depressurized. Then, the thermally decomposed solution is returned to the sample cup 11 by: the liquid is dropped into the sample cup 11 through the total nitrogen decomposition liquid discharge pipe L13 by Opening (ON) the 9 th and 2 nd normally-closed valves V11 and V2, and then the residual liquid in the total nitrogen decomposition pipe L6 is purged by operating the air pump P10 in a state where the 8 th normally-closed valve V8 is opened and the 2 nd three-way valve V10 is opened (the V8 side is closed).
The reason why the total nitrogen-measuring thermally decomposed liquid is returned through the total nitrogen decomposed liquid discharge pipe L13 is to prevent the unheated potassium peroxodisulfate solution remaining in the total nitrogen decomposition pipe L6 from being mixed into the thermally decomposed liquid. The unheated potassium peroxodisulfate solution is a component that interferes with the determination of total nitrogen.
By Opening (ON) the 3 rd normally-closed valve V3, the pyrolysis portion of the total phosphorus decomposition pipe L7 is depressurized. Then, the thermally decomposed solution is returned to the sample cup 11 by: the liquid is dropped into the sample cup 11 by Opening (ON) the 3 rd and 4 th normally-closed valves V3 and V4, and then the residual liquid in the total phosphorus decomposition pipe L7 is purged by operating the air pump P10 in a state where the 8 th normally-closed valve V8 is opened and the 2 nd three-way valve V10 is opened (the V8 side is closed).
The pyrolysis section is cleaned by flowing pure water to the pyrolysis section. Specifically, the pure water pump P8 performs the purge operation in a state where any one or more of the 1 st and 2 nd normally-closed valves V1 and V2, the 9 th and 2 nd normally-closed valves V11 and V2, or the 3 rd and 4 th normally-closed valves V3 and V4 are Opened (ON) and the 8 th normally-closed valve V8, the 1 st three-way valve V9, and the 2 nd three-way valve V10 are all closed.
Further, the operation of directly introducing pure water into the sample cup 11 for washing and dilution is performed as follows: the purge operation is performed by the deionized water pump P8 in a state where the 8 th normally-closed valve V8 is closed (OFF), the 1 st three-way valve V9 is closed (the 2 nd three-way valve V10 side is open), and the 2 nd three-way valve V10 is open (the downstream end side of the deionized water pipe L8 is open).
Before the cleaning or diluting operation is performed, the suction operation of the pure water pump P8 is performed with the 1 st three-way valve V9 opened (the pure water tank T8 side is opened), and the pure water pump P8 is filled with pure water.
The upstream end of the liquid discharge pipe L9 is inserted into the bottom of the sample cup 11. And the downstream end reaches a liquid discharge port of the device so as to discharge the liquid to be discharged to the outside of the device.
A drain pump P9 is provided in the middle of the drain pipe L9.
The measurement of the total phosphorus concentration by the analyzer of the present embodiment is performed by sequentially executing the following steps under the control of the control unit 30.
The control unit 30 stores a program for causing the control unit 30 to execute a process including the following steps.
The preparation method comprises the following steps: introducing a sample solution and a thermal decomposition reagent into a reaction tank, and transporting them from the reaction tank to a thermal decomposition unit;
step 1: subjecting the sample liquid to pyrolysis in a pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to a reaction tank;
and step 3: transporting the heated decomposition liquid or a liquid obtained by adding a predetermined reagent to the heated decomposition liquid from the reaction tank to the absorbance detection section as a blank solution;
and 4, step 4: measuring the absorbance of the blank solution in an absorbance detector;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section through the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: conveying the reheated blank solution from the thermal decomposition unit to a reaction tank;
and 8: reacting a color developing reagent with a blank solution in a reaction tank to obtain a color developing solution;
and step 9: transporting the color developing solution from the reaction tank to an absorbance detection section;
step 10: measuring the absorbance of the color developing solution in an absorbance detection unit;
step 11: the concentration of the measurement target component in the sample solution is determined from the difference between the absorbance of the color-developing solution obtained in step 10 and the absorbance of the blank solution obtained in step 4.
Next, a specific procedure for measuring the total phosphorus concentration and the total nitrogen concentration will be described. In addition, procedures corresponding to the above steps 1 to 11 in the measurement of the total phosphorus concentration are shown in parentheses.
1. Total nitrogen sample conditioning
First, a predetermined amount of a sample liquid is introduced into the sample cup 11 of the reaction vessel 10 through the sample liquid pipe L2. Here, deionized water is introduced into the sample cup 11 from the deionized water pipe L8 as necessary to dilute the sample liquid. Next, a sodium hydroxide solution in the 1 st reagent tank T1 and a potassium peroxodisulfate solution in the 2 nd reagent tank T2 as thermal decomposition reagents for measuring total nitrogen were introduced into the sample cup 11, and the sample solution and the thermal decomposition reagents were mixed to prepare a total nitrogen sample solution.
Then, the entire total nitrogen sample liquid is sucked into a portion (thermal decomposition unit) of the total nitrogen decomposition pipe L6 which is accommodated in the heating tank 13 (in a preheated state), and is kept on standby while the 1 st and 2 nd normally-closed valves V1 and V2 are closed (OFF) to adjust the total phosphorus sample.
2. Total phosphorus sample conditioning
After the inside of the sample cup 11 is cleaned, a predetermined amount of the sample liquid is introduced into the sample cup 11 through the sample liquid pipe L2. Here, deionized water is introduced into the sample cup 11 from the deionized water pipe L8 as necessary to dilute the sample liquid. Next, a potassium peroxodisulfate solution in the 2 nd reagent tank T2 as a thermal decomposition reagent for measuring total phosphorus was introduced into the sample cup 11, and the sample solution and the thermal decomposition reagent were mixed to prepare a total phosphorus sample solution.
Then, the entire total phosphorus sample liquid is sucked into a portion (thermal decomposition unit) of the total phosphorus decomposition pipe L7 which is accommodated in the heating tank 13 (in the preheated state), and the 3 rd normally-closed valve V3 and the 4 th normally-closed valve V4 are closed (preparation step).
3. Decomposition by heating
The pyrolysis section of the total nitrogen decomposition pipe L6 was pressurized, and then the pyrolysis section of the total phosphorus decomposition pipe L7 was pressurized.
Then, the temperature of the heating bath 13 was set to 120 ℃ and maintained for 30 minutes, and the total nitrogen sample liquid in the total nitrogen decomposition pipe L6 and the total phosphorus sample liquid in the total phosphorus decomposition pipe L7 were subjected to thermal decomposition to prepare a total nitrogen measurement thermal decomposition liquid and a total phosphorus measurement thermal decomposition liquid, respectively.
By decomposition by heating, all nitrogen compounds in the sample liquid are oxidized into nitrate ions. Furthermore, all the phosphorus compounds in the sample solution are oxidized into phosphate ions (step 1).
After the thermal decomposition, the respective thermal decomposition portions are depressurized.
4. Total nitrogen determination
After the pressure release, the heated decomposition liquid in the total nitrogen decomposition pipe L6 is returned to the sample cup 11 through the total nitrogen decomposition liquid discharge pipe L13. The heated decomposition liquid is moved from the heated decomposition portion heated by the heating bath 13 into the sample cup 11, and the temperature is promoted to be lowered to such an extent that the absorbance measurement can be performed by the absorbance detection portion 20 (left to cool).
Here, hydrochloric acid introduced into the 4 th reagent tank T4 is adjusted to a pH of 2 to 3 to obtain a liquid to be measured for total nitrogen measurement.
Next, the absorbance of the liquid to be measured for total nitrogen measurement is measured by the absorbance detector 20 according to the following procedure.
When the amount of the liquid to be measured in the sample cup 11 is small and it is necessary to perform a preliminary washing in the flow cell of the absorbance detection unit 20 with the liquid to be measured in the sample cup 11, the absorbance measurement by the absorbance detection unit 20 is performed according to the following procedures of step D1 to step D4.
If no prewashing is required, the procedure of steps D3 to D4 is followed.
Step D1: the detection pump P1 is driven in the forward direction to draw a part of the liquid to be measured in the sample cup 11 into the flow cell of the absorbance detection unit 20.
Step D2: the pump P1 for detection is driven in the reverse direction to return the liquid to be measured sucked into the flow cell into the sample cup 11.
Step D3: the detection pump P1 is driven in the forward direction to draw a part of the liquid to be measured in the sample cup 11 into the flow cell.
Step D4: the absorbance of the liquid to be measured is measured by the absorbance detector 20.
In step D1, the amount of the liquid to be measured sucked into the flow cell is the minimum amount necessary for the preliminary washing so as not to reach the buffer tank 15. On the other hand, since the amount of the liquid to be measured sucked into the flow cell in step D3 may reach the buffer tank 15 to some extent, the amount of the liquid to be measured is set to be larger than the amount of the liquid to be sucked in step D1 and the entire flow cell 21 can be reliably filled with the liquid to be measured.
The absorbance is measured using a wavelength corresponding to the concentration of the nitrate ion and a wavelength corresponding to the amount of the turbidity component or the like without absorbing the nitrate ion. Then, the total nitrogen concentration of the sample liquid is determined from the measurement results of the two wavelengths and the previously determined calibration curve information.
For example, japanese environmental hall (current environmental province) in 1974 announces No. 64 and JIS K0102: 2016 (45) to measure the absorbance at each wavelength of 220nm, which corresponds to the nitrate ion concentration, and 254nm, which corresponds to the amount of the turbid component without absorbing the nitrate ion, and calculate the total nitrogen concentration of the sample liquid by subtracting the absorbance at 254nm from the absorbance at 220nm based on the previously determined calibration curve information.
Further, in the Chinese standards "HJ/T102-2003" and "GB 11894-89", the total nitrogen concentration of the sample liquid was determined by measuring the absorbance at each wavelength of 220nm, which corresponds to the concentration of the nitrate ion, and 275nm, which corresponds to the amount of the turbid component without absorbing the nitrate ion, and by converting the value obtained by subtracting 2 times the absorbance at 275nm from the absorbance at 220nm based on the previously determined calibration curve information.
After the absorbance measurement, the detection pump P1 was further driven in the forward direction to discharge the entire measurement target liquid in the sample cup 11 into the waste liquid tank T7. Then, the detection pipe L1 is cleaned as necessary. When the detection pipe L1 is cleaned, the detection pump P1 is driven in the forward direction after the washing water is introduced into the sample cup 11, and the washing water in the sample cup 11 is drained into the waste liquid tank T7, whereby the detection pipe L1 is cleaned.
The cleaning water is preferably water discharged into the sample cup 11 after cleaning the total nitrogen decomposition pipe L6 with pure water.
Accordingly, the total nitrogen decomposition pipe L6, the sample cup 11, and the detection pipe L1 can all be cleaned.
After the interior of the detection pipe L1 is sufficiently cleaned, the detection pump P1 is driven in reverse to return the washing water remaining in the buffer tank 15 of the detection pipe L1 to the sample cup 11, and the washing water remaining in the sample cup 11 is discharged from the discharge pipe L9.
5. Total phosphorus determination
The thermally decomposed solution in the decomposition pipe L7 for total phosphorus is returned to the sample cup 11 (step 2). The heated decomposition liquid is moved from the heated decomposition portion heated by the heating bath 13 into the sample cup 11, and the temperature is promoted to be lowered to such an extent that the absorbance measurement can be performed by the absorbance detection portion 20 (left to cool). Here, a blank solution to which the L-ascorbic acid solution of the 3 rd reagent kit T3 was added was obtained as a solution to be measured.
Next, in the absorbance detection section 20, the absorbance at a wavelength (described in detail later) corresponding to the molybdenum blue based on the phosphate ions is measured using the blank solution as a measurement target solution.
When the amount of the liquid to be measured in the sample cup 11 is small and it is necessary to perform the preliminary washing in the flow cell of the absorbance detector 20 with the liquid to be measured in the sample cup 11, the absorbance measurement by the absorbance detector 20 is performed according to the procedures of step D1, step D2, step D3 (step 3), and step D4 (step 4) described above.
If no prewashing is needed, the procedure is followed from the step D3 (step 3) to the step D4 (step 4).
However, since it is necessary to return the blank solution to the sample cup 11 again, the amount of the liquid to be measured sucked into the flow cell in step D3 is the minimum amount necessary for performing the preliminary washing so as not to reach the buffer tank 15, as in step D1.
Then, the detection pump P1 is driven in reverse without discarding the blank solution, and the liquid to be measured sucked into the flow cell is returned into the sample cup 11.
The blank solution returned to the sample cup 11 is sucked by the pure water pump P8 to the portion (pyrolysis unit) of the total phosphorus decomposition pipe L7 which is accommodated in the heating tank 13 (preheated state) (step 5), and is stopped in the pyrolysis unit to be reheated by preheating of the pyrolysis unit (step 6).
Thereafter, similarly to the case of returning the thermally decomposed solution to the sample cup 11, the reheated blank solution is returned to the sample cup 11 (step 7), and the ammonium molybdate solution in the 5 th reagent tank T5 is introduced thereinto to obtain a color developing solution in which molybdenum blue is formed as a liquid to be measured (step 8).
Next, in the absorbance detection section 20, the absorbance at a wavelength (described later in detail) corresponding to the molybdenum blue based on the phosphate ions is measured using the color developing solution as the measurement target solution.
When the amount of the liquid to be measured in the sample cup 11 is small and it is necessary to perform the preliminary washing in the flow cell of the absorbance detector 20 with the liquid to be measured in the sample cup 11, the absorbance measurement by the absorbance detector 20 is performed according to the procedures of step D1, step D2, step D3 (step 9), and step D4 (step 10) described above.
If no prewashing is needed, the procedure is followed from step D3 (step 9) to step D4 (step 10).
For example, japanese environmental hall (current environmental province) in 1974 announces No. 64 and JIS K0102: 201646.3, since the wavelength 800nm is used as the wavelength corresponding to molybdenum blue, the total phosphorus concentration of the sample solution is determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the developing solution having the wavelength 800nm based on the previously determined calibration curve information.
In addition, since the wavelength 700nm is adopted as the wavelength corresponding to molybdenum blue in the Chinese standards "HJ/T102-2003" and "GB 11893-89", the total phosphorus concentration of the sample solution is determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the developing solution having the wavelength 700nm, based on the previously determined calibration curve information.
After the absorbance of the liquid to be measured, which is the color developing solution, is measured, the detection pump P1 is driven in the forward direction, and the entire liquid to be measured in the sample cup 11 is discarded into the waste liquid tank T7. Next, after the introduction of the washing water into the sample cup 11, the detection pump P1 is driven in the forward direction, whereby the washing water in the sample cup 11 is discarded into the waste liquid tank T7, and the detection pipe L1 is washed.
The washing water W is preferably water discharged into the sample cup 11 after washing the total phosphorus decomposition pipe L7 with pure water.
Thus, the total phosphorus decomposition pipe L7, the sample cup 11, and the detection pipe L1 can all be cleaned.
After the interior of the detection pipe L1 is sufficiently cleaned, the detection pump P1 is driven in reverse to return the washing water remaining in the buffer tank 15 of the detection pipe L1 to the sample cup 11, and the washing water remaining in the sample cup 11 is discharged from the discharge pipe L9.
Fig. 2 is a diagram summarizing an analysis method using the analysis device according to the present embodiment. In the analysis apparatus, Total Nitrogen (TN) analysis and Total Phosphorus (TP) analysis are performed, and the analysis of Total Phosphorus (TP) is the analysis method of the present invention.
Specifically, a potassium peroxodisulfate solution as a thermal decomposition reagent was added to a sample solution and heated at 120 ℃ for 30 minutes to effect thermal decomposition, and a predetermined reagent, L-ascorbic acid solution, was added to the resulting thermal decomposition solution to obtain a liquid, and the absorbance at 700nm of the blank solution was measured using the liquid as a blank solution. After that, the blank solution was heated again, and then an ammonium molybdate solution as a reagent for developing color was added to the blank solution to perform a reaction to obtain a color developing solution, and the absorbance at 700nm of the obtained color developing solution was measured.
According to the analysis method of the analyzer of the present embodiment, even if the temperature of the blank solution returned to the sample cup 11 is too low due to a low ambient temperature, the reaction of producing molybdenum blue from the ammonium molybdate solution is promoted by reheating, and the color development corresponding to the concentration of phosphate ions produced by thermal decomposition is obtained. Therefore, the total phosphorus concentration can be accurately measured even when the ambient temperature is low.
< analysis device of other embodiment >
The analyzer according to another embodiment of the present invention may be configured as a total chromium analyzer. For example, a total chromium analyzing apparatus can be manufactured by connecting a reagent supply pipe for a sulfuric acid solution and a reagent supply pipe for a sodium peroxodisulfate solution to the 1 st reagent discharge pipe L3 of fig. 1, connecting a reagent supply pipe for a diphenylcarbazide solution to the 2 nd reagent discharge pipe L4, and omitting the 3 rd reagent discharge pipe L5.
The total chromium analyzer of the present embodiment operates in the same manner as the total nitrogen and total phosphorus analyzers described above, and thus can measure the total chromium concentration.
Fig. 3 is a diagram summarizing the analysis method using an analyzer configured as a total chromium analyzer.
Specifically, a sodium peroxodisulfate solution and a sulfuric acid solution as thermal decomposition reagents were added to a sample solution, and the mixture was heated at 120 ℃ for 20 minutes to effect thermal decomposition, and then left to cool, and the resulting thermal decomposition solution was used as a blank solution to measure the absorbance of the blank solution at 525 nm. Subsequently, the blank solution was reheated, and then a diphenylcarbazide solution as a color developing reagent was added to the blank solution to carry out a reaction to obtain a color developing solution, and the absorbance at 525nm of the obtained color developing solution was measured.
The total chromium concentration of the sample solution was determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the 525nm developing solution based on the previously determined calibration curve information.
The analyzer according to another embodiment of the present invention may be configured as a total copper analyzer. For example, the total copper analyzer can be obtained by connecting a reagent supply line for a sulfuric acid solution, a reagent supply line for a sodium peroxodisulfate solution, and a reagent supply line for a hydroxylamine hydrochloride solution to the 1 st reagent discharge line L3 in fig. 1, connecting a reagent supply line for a mixed solution of alkaline sodium copper phosphate and sodium acetate to the 2 nd reagent discharge line L4, and omitting the 3 rd reagent discharge line L5.
The total copper concentration can be measured by operating the total copper analyzer of the present embodiment in the same manner as the total nitrogen and total phosphorus analyzers.
Fig. 4 is a diagram summarizing an analysis method using an analyzer configured as a total copper analyzer.
Specifically, a sodium peroxodisulfate solution and a sulfuric acid solution as thermal decomposition reagents were added to a sample solution, the mixture was heated at 120 ℃ for 20 minutes to effect thermal decomposition, the mixture was left to cool, a hydroxylamine hydrochloride solution as a predetermined reagent was added to the obtained thermal decomposition solution to obtain a liquid, and the absorbance at 470nm of the blank solution was measured using the liquid as a blank solution. After that, the blank solution was reheated, a mixed solution of alkaline sodium copper phosphate and sodium acetate as a color-developing reagent was added to the blank solution to perform a reaction to obtain a color-developing solution, and the absorbance at 470nm of the obtained color-developing solution was measured.
The total copper concentration of the sample solution was determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the developing solution at 470nm based on the previously determined calibration curve information.
The analyzer according to another embodiment of the present invention may be configured as a total nickel analyzer. For example, the total nickel analyzer can be obtained by connecting a reagent supply pipe for a mixed solution of sulfuric acid and potassium hydrogen peroxymonosulfate (Oxone) and a reagent supply pipe for a mixed solution of sodium formate and sodium hydroxide and a mixed solution of citric acid and ammonium peroxydisulfate to the 1 st reagent discharge pipe L3 in fig. 1, connecting a reagent supply pipe for a mixed solution of dimethylglyoxime and sodium hydroxide to the 2 nd reagent discharge pipe L4, and omitting the 3 rd reagent discharge pipe L5.
The total nickel analyzer of the present embodiment operates in the same manner as the total nitrogen and total phosphorus analyzers, and thereby can measure the total nickel concentration.
Fig. 5 is a diagram summarizing an analysis method using an analyzer configured as a total nickel analyzer.
Specifically, a mixed solution of sulfuric acid and potassium hydrogen peroxymonosulfate (Oxone) as a thermal decomposition reagent was added to a sample solution, the mixture was heated at 120 ℃ for 20 minutes to perform thermal decomposition, the mixture was left to cool, a mixed solution of sodium formate and sodium hydroxide as a predetermined reagent and a mixed solution of citric acid and ammonium peroxydisulfate were added to the obtained thermal decomposition solution to obtain a liquid, and the absorbance at 470nm of the blank solution was measured using the liquid as a blank solution. After the blank solution was reheated, a mixed solution of dimethylglyoxime and sodium hydroxide as a reagent for developing color was added to the blank solution to perform a reaction to obtain a color developing solution, and the absorbance at 470nm of the obtained color developing solution was measured.
The total nickel concentration of the sample solution was determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the developing solution at 470nm based on the previously determined calibration curve information.
The analyzer according to another embodiment of the present invention may be configured as a total manganese analyzer. For example, a nitric acid solution supply line, a monoethanolamine solution supply line, and a formaldoxime solution are connected to the 1 st reagent discharge line L3 of FIG. 1EDTA2 Na.2H is connected to the liquid reagent supply pipe and the 2 nd reagent discharge pipe L42The total manganese analysis apparatus can be manufactured by omitting the 3 rd reagent discharge pipe L5 and the reagent supply pipe for the mixed solution of O and hydroxylamine hydrochloride.
The total manganese concentration can be measured by operating the total manganese analyzer of the present embodiment in the same manner as the total nitrogen and total phosphorus analyzers.
Fig. 6 is a diagram summarizing an analysis method using an analyzer configured as a total manganese analyzer.
Specifically, a nitric acid solution as a thermal decomposition reagent was added to the sample solution, and the mixture was heated at 120 ℃ for 12 minutes to perform thermal decomposition, and then left to cool, and the obtained thermal decomposition solution was used as a blank solution, and the absorbance at 470nm of the blank solution was measured. Thereafter, the blank solution was reheated, and then monoethanolamine solution, formaldoxime solution and EDTA2Na & 2H as a coloring reagent were added to the blank solution2A mixed solution of O and hydroxylamine hydrochloride was reacted to obtain a color developing solution, and the absorbance at 470nm of the obtained color developing solution was measured.
The total manganese concentration of the sample solution was determined by converting the value obtained by subtracting the absorbance of the blank solution from the absorbance of the developing solution at 470nm based on the previously determined calibration curve information.
In any of the above embodiments, when the ambient temperature is sufficiently high, reheating may not be performed. For example, the ambient temperature may be measured, and the reheating may be performed only when the ambient temperature is equal to or lower than a certain temperature.
< procedure, etc. >
In the above embodiment, an example of the operation according to the program stored in the control unit 30 of the analysis device is shown. However, a part or all of the functions of the control unit 30 in the analyzer according to the present invention may be carried by an external computer connected directly to the analyzer or connected via a communication system.
In this case, the program may be stored in the computer in advance, or may be stored in a storage medium readable by the computer and the program stored in the storage medium may be read by the computer.
Further, a program stored in advance in a computer and a program stored in a computer-readable storage medium and read by the computer may be used in combination.
Further, either or both of the program stored in advance in the computer and the program stored in a computer-readable storage medium and read by the computer may be used in combination with the program stored in the control unit 30 of the analysis device.
Claims (5)
1. An analysis device, comprising:
a thermal decomposition unit; a reaction tank in which a liquid is movable between the reaction tank and the pyrolysis section; an absorbance detecting section for allowing a liquid to move between the absorbance detecting section and the reaction tank; and a control part for controlling the operation of the motor,
the following steps are sequentially executed by the control of the control part:
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: transporting the thermal decomposition liquid or a liquid obtained by adding a predetermined reagent to the thermal decomposition liquid, as a blank solution, from the reaction tank to the absorbance detection unit;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting a color-developing reagent with the blank solution in the reaction tank to obtain a color-developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: the absorbance detection unit measures the luminosity of the color developing solution.
2. The analysis device according to claim 1,
the step 1 is performed after introducing a sample solution and a pyrolysis reagent into the reaction vessel and transporting them from the reaction vessel to the pyrolysis section.
3. An analysis device, comprising:
a thermal decomposition unit; a reaction tank in which a liquid is transferred between the reaction tank and the pyrolysis unit; an absorbance detection unit for transferring a liquid between the reaction tank and the liquid transport unit; and a control part for controlling the operation of the motor,
the following steps are sequentially executed by the control of the control part:
the preparation method comprises the following steps: introducing a sample solution and a potassium peroxodisulfate solution into the reaction tank, and transporting them from the reaction tank to the thermal decomposition unit;
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: a step of transferring a liquid obtained by adding an L-ascorbic acid solution to the heated decomposition liquid from the reaction tank to the absorbance detection unit as a blank solution;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting an ammonium molybdate solution with the blank solution in the reaction tank to obtain a color developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: measuring the absorbance of the color developing solution in the absorbance detection unit;
step 11: and (4) determining the total phosphorus concentration of the sample solution according to the difference between the absorbance of the color developing solution obtained in the step (10) and the absorbance of the blank solution obtained in the step (4).
4. A program, characterized in that,
causing a control section of an analysis device provided with a thermal decomposition section, a reaction tank in which a liquid is movable between the thermal decomposition section and the reaction tank, an absorbance detection section in which a liquid is movable between the reaction tank and the reaction tank, and the control section to execute a process including:
step 1: subjecting the sample liquid to pyrolysis in the pyrolysis section to obtain a pyrolysis liquid;
step 2: transporting the heated decomposition liquid from the heated decomposition portion to the reaction tank;
and step 3: transporting the thermal decomposition liquid or a liquid obtained by adding a predetermined reagent to the thermal decomposition liquid, as a blank solution, from the reaction tank to the absorbance detection unit;
and 4, step 4: measuring the absorbance of the blank solution in the absorbance detection unit;
and 5: transporting the blank solution from the absorbance detection section to the thermal decomposition section via the reaction tank;
step 6: reheating the blank solution in the pyrolysis section;
and 7: transporting the reheated blank solution from the thermal decomposition unit to the reaction tank;
and 8: reacting a color-developing reagent with the blank solution in the reaction tank to obtain a color-developing solution;
and step 9: transporting the color developing solution from the reaction tank to the absorbance detection section;
step 10: the absorbance of the color-developing solution is measured by the absorbance detection unit.
5. A method for analyzing a sample liquid, comprising using a heated decomposition liquid obtained by subjecting a sample liquid to thermal decomposition or a liquid obtained by adding a predetermined reagent to the heated decomposition liquid as a blank solution, measuring the absorbance of the blank solution, reacting a color-developing reagent with the blank solution to obtain a color-developing liquid, and measuring the absorbance of the obtained color-developing liquid,
the method for analyzing a sample liquid is characterized in that,
after the absorbance of the blank solution is measured, the blank solution is reheated before the color developing reagent is reacted with the blank solution.
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| CN202442960U (en) * | 2012-01-21 | 2012-09-19 | 东亚Dkk株式会社 | Total nitrogen determinator, total phosphorus determinator and sample water introduction device |
| CN103994996A (en) * | 2014-06-11 | 2014-08-20 | 攀枝花学院 | Analysis method for phosphorus in ferrovanadium |
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| US5240681A (en) * | 1990-10-15 | 1993-08-31 | Calgon Corporation | Apparatus for injection analysis of total inorganic phosphate |
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| JP3643429B2 (en) * | 1996-03-08 | 2005-04-27 | 株式会社日立製作所 | Chemical analyzer |
| JP4691266B2 (en) * | 2001-04-18 | 2011-06-01 | 株式会社 堀場アドバンスドテクノ | Total nitrogen and / or total phosphorus measuring device |
| JP4044399B2 (en) * | 2002-09-03 | 2008-02-06 | 東亜ディーケーケー株式会社 | Total nitrogen / total phosphorus measurement device and sample water introduction device |
| JP4893864B2 (en) * | 2010-07-21 | 2012-03-07 | 三浦工業株式会社 | Determination of total phosphorus |
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| CN202442960U (en) * | 2012-01-21 | 2012-09-19 | 东亚Dkk株式会社 | Total nitrogen determinator, total phosphorus determinator and sample water introduction device |
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