JP2010286427A - Sulfur and total sulfur measuring method, measuring system, and solid polymer electrolyte fuel cell (pefc) - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfur and total sulfur measuring method etc., avoiding measurement sensitivity problems caused by absorption by air in measurements by a total sulfur ICP method on water for humidifiers supplied to a polymer electrolyte membrane of a solid Polymer Electrolyte Fuel Cell (PEFC). <P>SOLUTION: A sulfur component in an extract 31 extracted from water for humidifiers is measured by a Inductively-Coupled Plasma (ICP) emission analysis method using a spectroscopic/photometric part 22 in which the inside is substituted with an inert gas to evaluate water quality components. A sulfur quantitative analysis line (S=180.734 nm) has an emission line wavelength of 185 nm or below. Since absorption by oxygen in the air at measurement happens on the short wavelength side of an emission line 38 of 200 nm or below, it is applied to substitute the inside of the spectroscopic/photometric part 22 with nitrogen gas, the inert gas, to expel oxygen. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a humidifier comprising a sulfur-based ionic species of an inorganic compound and sulfur of an organic compound component, which is supplied from a humidifier to a polymer electrolyte membrane of a polymer electrolyte fuel cell (PEFC). The present invention relates to a sulfur and total sulfur measurement method for evaluating water quality components of irrigation water.

  Generally, quantification of “elution components of fuel cell hollow fiber humidifier module water (hereinafter referred to as“ humidifier water ”) containing sulfur-based ionic species of inorganic compounds and ionic components derived from sulfur of organic compounds. The analysis has a problem of corrosion to the material due to the water quality of all sulfur compounds, so it is necessary to consider the analysis investigation. In addition, there is an increasing need for analysis of sulfur-based gas problems in the air environment, investigation of sulfur contamination related to gas sensors, and analysis of water quality of sulfur-based ionic components of treated water. Has been done. In these water quality analysis surveys, etc., sulfur and total sulfur analysis and organic component analysis are performed, and further, evaluation is performed by analysis methods of pH, conductivity, anion, cation component and heavy metal component.

  In the method for quantitative determination of sulfur, S = 180.734 nm by plasma emission analysis (inductively coupled plasma (ICP method)) is a rapid and accurate method. However, since the emission wavelength is absorbed by air in the vacuum ultraviolet region, there is a problem of sensitivity. For this reason, it is necessary to examine the measurement conditions, but this is not generally done. Therefore, if an analysis method can be established, it is considered that analysis and evaluation of total sulfur can be performed quickly and accurately.

Fluororesin ion exchange membranes are used for polymer electrolyte membranes of polymer electrolyte fuel cells (PEFC). Since this polymer electrolyte membrane exhibits high H ⁺ ion conductivity only in a wet state, a humidifier water for supplying water to the polymer electrolyte membrane is necessary. For this reason, in order to realize a high-performance solid polymer electrolyte fuel cell (PEFC), it is important to establish an appropriate management method for humidifier water supplied to the polymer electrolyte membrane. In other words, it is important to evaluate the quality of water components in humidifier water by evaluating the presence or absence of eluents that affect the performance of the polymer electrolyte fuel cell (PEFC), and the pH, conductivity, anion, In addition to the cationic and heavy metal components, there is a particular need for a method for the determination of sulfur and total sulfur.

  In the measurement of sulfur in the vacuum ultraviolet region by the ICP method, it is said that a total emission spectrum of 166 nm to 847 nm can be obtained by measurement (see Non-Patent Document 1). However, as described above, there is a problem of sensitivity due to absorption by air in measurement. Therefore, there is a problem that the contents described in Non-Patent Document 1 cannot be directly applied to the evaluation of the water quality component of the humidifier water of the polymer electrolyte fuel cell (PEFC). Further, Non-Patent Document 1 does not describe details of the measurement method.

  As a method for measuring the concentration of total sulfur, (1) flask combustion-titration method, (2) flask combustion-ion chromatograph method, (3) measurement method by microcurrent titration method, etc. are generally applied (non-patent) Reference 2). However, since these measurement methods are intended for solids or powders, it is necessary to make a solution and process a large amount of sample. For this reason, it is difficult to measure a trace amount of several ppm level, and in addition, since the time required for decomposition and measurement is long, it can be applied as it is to the evaluation of the water quality components of water for humidifiers of polymer electrolyte fuel cells (PEFC). There was a problem that I could not.

There is a method that aims to provide a sulfur component measuring device that can quickly and accurately measure total sulfur, sulfuric acid mist, and SO ₂ gas components by switching the flow path (see Patent Document 1). In Patent Document 1, by operating the flow path switching means provided in the sample line and the reference line, the total sulfur, sulfuric acid mist, and SO ₂ gas components are respectively appropriately calculated by the difference calculation by a single analyzer. It is structured so that it can be obtained quickly. However, since the technique described in Patent Document 1 traps an inorganic component targeting a gas component, it does not target a humidifier water that is an extract. That is, the technique described in Patent Document 1 includes an ionic species of an inorganic compound and an ionic component derived from sulfur of an organic compound, and is supplied to supply a water to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC). It is not intended for humidifier water and does not relate to measurement and evaluation of water quality components. Therefore, there is a problem that it cannot be applied as it is to the evaluation of the water component of the humidifier water of the polymer electrolyte fuel cell (PEFC).

  There is an ion quantitative analysis method for finding a component derived from a polymer electrolyte membrane material in discharged water of a solid polymer electrolyte fuel cell (PEFC) (see Patent Document 2). However, the technique described in Patent Document 2 is not related to the evaluation of the water quality component of the water for the humidifier of the polymer electrolyte fuel cell (PEFC).

  As described above, the technique described in Non-Patent Document 1 has a problem of sensitivity because it is absorbed by measurement air. Therefore, there is a problem that the contents described in Non-Patent Document 1 cannot be directly applied to the evaluation of the water quality component of the humidifier water of the polymer electrolyte fuel cell (PEFC).

  As described above, since the measurement method described in Non-Patent Document 2 targets a solid or a powder, it is necessary to make a solution and process a large amount of sample. For this reason, it is difficult to measure a trace amount of several ppm level, and in addition, since the time required for decomposition and measurement is long, it is applied as it is to the evaluation of the water quality component of the water for the humidifier of the polymer electrolyte fuel cell (PEFC). There was a problem that I could not.

  As described above, since the technique described in Patent Document 1 traps an inorganic component targeting a gas component, it includes an ionic species of an inorganic compound and an ionic component derived from sulfur of an organic compound, and is solid. It is not intended for humidifier water supplied for supplying water to a polymer electrolyte membrane of a polymer electrolyte fuel cell (PEFC), and does not relate to measurement and evaluation of water quality components. Therefore, there is a problem that it cannot be applied as it is to the evaluation of the water component of the humidifier water of the polymer electrolyte fuel cell (PEFC).

  As described above, since the technique described in Patent Document 2 is an ion quantitative analysis method for finding a component derived from a polymer electrolyte membrane material in the discharged water of a solid polymer electrolyte fuel cell (PEFC), the solid polymer electrolyte type There has been a problem that it cannot be applied as it is to the evaluation of the water quality of humidifier water for fuel cells (PEFC).

  Accordingly, a first object of the present invention has been made to solve the above problems, and is supplied to a polymer electrolyte membrane in order to realize a high-performance solid polymer electrolyte fuel cell (PEFC). The purpose is to establish an appropriate management method for humidifier water. Specifically, the presence or absence of eluents that affect the performance of the polymer electrolyte fuel cell (PEFC) is evaluated. In addition to pH, conductivity, anion, cation component and heavy metal component, sulfur and The purpose is to establish a method for measuring total sulfur.

  The second object of the present invention is due to the absorption by air in the measurement in the ICP method of total sulfur for humidifier water supplied to the polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC). It is an object of the present invention to provide a method for measuring sulfur and total sulfur that can avoid the problem of sensitivity.

  The third object of the present invention is to accurately determine sulfur-derived ionic species of inorganic compounds in the ion chromatography method for humidifier water supplied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC). An object of the present invention is to provide a method for measuring sulfur and total sulfur which can be measured well and in a short time.

  The fourth object of the present invention is to measure organic compounds derived from sulfur in gas chromatography / mass spectrometry for humidifier water supplied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC). An object of the present invention is to provide a method for measuring sulfur and total sulfur that can be measured by gas chromatography / mass spectrometry.

  The method for measuring sulfur and total sulfur according to the present invention is supplied from a humidifier to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing a sulfur type ionic species of an inorganic compound and sulfur of an organic compound component. A method for measuring sulfur and total sulfur in water quality component measurement of humidifier water, wherein the structural material used in the humidifier consists of an organic film, and the sulfur component in the extract extracted from the humidifier water, A water quality component is evaluated by measuring by inductively coupled plasma (ICP) emission spectrometry using a spectrometer in which the inside is replaced with an inert gas.

  The method for measuring sulfur and total sulfur according to the present invention is supplied from a humidifier to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing a sulfur type ionic species of an inorganic compound and sulfur of an organic compound component. A method for measuring sulfur and total sulfur in measuring water quality components of humidifier water, wherein the structural material used in the humidifier is an organic film, and the inorganic compound contained in the structural material in the humidifier water is water-soluble. It is characterized by extracting a water-soluble ion component with pure water and simultaneously analyzing and measuring sulfur-derived ion species by an ion chromatography method to evaluate a water quality component.

  The method for measuring sulfur and total sulfur according to the present invention is supplied from a humidifier to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing a sulfur type ionic species of an inorganic compound and sulfur of an organic compound component. This is a method for measuring sulfur and total sulfur in the measurement of water quality components in humidifier water, wherein the structural material used in the humidifier consists of an organic film, and the organic compound components in the humidifier water are analyzed by solid-phase microextraction. It is characterized by extracting, measuring organic compounds derived from sulfur by gas chromatography / mass spectrometry, and evaluating water quality components.

  The method for measuring sulfur and total sulfur according to the present invention is characterized by performing each water quality component evaluation in the method for measuring sulfur and total sulfur according to the present invention, and analyzing the total sulfur based on these results to evaluate the water quality component. And

  The measurement system of the present invention includes a humidifier that is a target of the measurement method of each water quality component evaluation in the sulfur and total sulfur measurement method of the present invention, a sampling port used for the measurement method, and a condensed water tank. Features.

  A solid polymer electrolyte fuel cell (PEFC) according to the present invention is characterized by using water for a humidifier controlled by a measuring method of each water quality component evaluation in the measuring method of sulfur and total sulfur of the present invention. .

  According to the method for measuring sulfur and total sulfur of the present invention, a humidifier is applied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of an inorganic compound and sulfur of an organic compound component. In the method of measuring sulfur and total sulfur in the measurement of water quality components of water for humidifiers supplied from the structural material used in the humidifier is an organic membrane, the sulfur component in the extract extracted from the water for humidifiers, The water quality component is evaluated by measuring by inductively coupled plasma (ICP) emission spectrometry using a spectroscopic / photometric part in which the inside is replaced with an inert gas. As a result, in the measurement by the ICP method of total sulfur for the humidifier water supplied to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC), the sensitivity problem due to the absorption by the air in the measurement is avoided. And a method for measuring sulfur and total sulfur can be provided. That is, there is an effect that it was possible to establish a microquantitative method capable of performing “analysis of total sulfur compounds” composed of inorganic and organic systems by ICP method at a lower limit of quantification of 1 ppm or less (lower limit of quantification = 50 ppb). .

  According to the method for measuring sulfur and total sulfur of the present invention, a humidifier is applied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of an inorganic compound and sulfur of an organic compound component. In the method for measuring sulfur and total sulfur in the measurement of water quality components of water for humidifiers supplied from, the structural material used in the humidifier is an organic film, and the inorganic compound contained in the structural material in the humidifier water is water-soluble Extraction of ionic components with pure water and simultaneous analysis and measurement of sulfur-derived ionic species by ion chromatography to evaluate water quality components. This is to perform quantitative analysis of sulfur components, and to separate and quantitatively analyze ionic species, providing an effect of providing a method for analyzing sulfur-derived polyvalent components such as sulfate ions and sulfite ions. It is done. In addition, the relationship between the peak area composed of the conductivity of the detected ion species and the concentration (eg, ppm) is made a calibration curve, and 14 components other than the sulfur-derived ion species are analyzed by applying in the same manner as this. You can also As a result, in the measurement by ion chromatography for the humidifier water supplied to the polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC), the sulfur-derived ionic species of inorganic compounds can be measured accurately and in a short time. It is possible to provide a method for measuring sulfur and total sulfur that can be performed.

  According to the method for measuring sulfur and total sulfur of the present invention, a humidifier is applied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of an inorganic compound and sulfur of an organic compound component. In the method for measuring sulfur and total sulfur in the measurement of the water quality components of humidifier water supplied from, the structural material used in the humidifier is an organic film, and the organic compound components in the humidifier water are extracted by solid-phase microextraction Extract and measure sulfur-derived organic compounds by gas chromatography / mass spectrometry to evaluate water quality components. For example, mercaptobenzothiazole, trimethylsilanol, polyphenylsulfone, and the like can be detected as sulfur components from detection and discrimination of many types of components, and the effect of providing an analysis method for organic compound components can be obtained. As a result, in the measurement by ion chromatography for the humidifier water supplied to the polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC), the sulfur-derived ionic species of inorganic compounds can be measured accurately and in a short time. It is possible to provide a method for measuring sulfur and total sulfur that can be performed. Thus, there is an effect that the sulfur-derived organic component obtained by extracting the sample hollow fiber humidifier module water with pure water can be analyzed and measured to establish a quantitative analysis of the sulfur component.

  According to the method for measuring sulfur and total sulfur of the present invention, the water quality components in the sulfur and total sulfur measurement methods of Examples 1 to 3 are evaluated together, and based on these results, the total sulfur is analyzed to analyze the water quality components. Make an evaluation. An effect is obtained that sulfur is measured by ICP emission analysis, and the component concentration is measured with the sample solution at an emission line intensity of 180.734 nm, for example. The emission line wavelength of this sulfur (S = 180.734 nm) is in the vacuum ultraviolet region, and measurement conditions such as nitrogen substitution in the spectroscopic / photometric part are performed. The analytical inspection method can obtain the effect of a quantitative analysis method performed by applying a calibration curve to the relationship between emission intensity and sulfur concentration (eg, ppm). Furthermore, in the ICP emission analysis method, other elements as well as sulfur can be obtained by examining the analysis conditions of components including pH, conductivity, ionic components, and heavy metals, and the water quality component evaluation of the hollow fiber humidifier module water can be performed. The effect that it is possible is also acquired. As a result, the water quality analysis and evaluation method including components such as sulfur eluted in the humidifier water from the polymer electrolyte fuel cell (PEFC) is sulfur analysis by ICP emission analysis and sulfur of inorganic compounds by ion chromatography. There is an effect that the component according to the form of the organic compound by the ion species derived from and the gas chromatography and mass spectrometry can be established.

  According to the measurement system or the like of the present invention, in the gas line supplied from the humidifier to the PEFC anode and the kassort side, the water for the humidifier is collected to the condensed water tank through the sample collection port. During normal operation, the sampling port is closed, and the time period during which the amount of power used is low is selected and opened to collect the humidifier water. The measuring method of each water quality component evaluation in the measuring method of sulfur of this invention and the total sulfur is implemented for the humidifier water collected in the condensed water tank. As a result, in this measurement system, proper management of humidifier water supplied to the polymer electrolyte membrane is performed, so that a high-performance solid polymer electrolyte fuel cell (PEFC) can be realized. . In other words, for the humidifier water extracted from the humidifier, the measurement method for evaluating each water component in the method for measuring sulfur and total sulfur according to the present invention is carried out, whereby a solid polymer electrolyte fuel cell (PEFC) ) Is capable of maintaining high-performance driving. That is, it is possible to realize a high-performance solid polymer electrolyte fuel cell (PEFC) using water for a humidifier controlled by the measurement method for evaluating each water component in the sulfur and total sulfur measurement method of the present invention. There is an effect that can be done.

It is a figure which shows the procedure of the measuring method of the sulfur used in common in each Example mentioned later and total sulfur. 1 is a schematic diagram of a configuration of an ICP emission analyzer 30. FIG. It is a block diagram of the ICP emission analysis apparatus 30 shown by FIG. It is a figure which shows the calibration curve relationship of ICP emitted light intensity (cpc) (vertical axis) and S concentration (ppm) (horizontal axis) which the inventor examined by said measurement conditions. 2 is a flow chart of ion chromatography in Example 2. FIG. 2 is a schematic diagram of ion chromatography in Example 2. FIG. It is a figure which shows the example of an anion chromatogram. It is a schematic diagram of the gas chromatography and mass spectrometry 14 (GC / MS). It is a figure which shows the example of analysis TIC (total ion chromatogram) of GC-MS. It is a diagram showing a relationship between SO ₄ ^2-major components of the test (first time) and Run 2. It is a figure which shows the relationship of the main component of the total sulfur of a test (1st time) and (2nd time). It is a figure which shows the measurement system 90 in Example 5. FIG.

  FIG. 1 shows the procedure of a method for measuring sulfur and total sulfur commonly used in each of the examples described later. In FIG. 1, reference numeral 11 is a water quality component measurement sample (organic membrane extract: PEFC humidifier water example), 12 is measured by ICP emission analysis (example of total sulfur analysis), and 13 is measured by ion chromatography ( Example of sulfur analysis by morphological ion species), 14 is measurement by gas chromatography / mass spectrometry (example of sulfur analysis by organic compound), and 15 is data arrangement (total sulfur analysis, etc.). The water quality component measurement sample 11 (PEFC humidifier water) is collected by sealing the humidifier module. Hereinafter, each embodiment will be described in detail with reference to the drawings.

  In Example 1, the water quality component of the water for the humidifier supplied from the humidifier to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC) containing the sulfur type ion species of the inorganic compound and sulfur of the organic compound component An example using the ICP emission analysis method 12 will be described as a method for measuring sulfur and total sulfur in the measurement. Here, the structural material used in the humidifier is made of an organic film. First, the ICP emission analysis method 12 will be described.

[About ICP emission analysis method 12: Sulfur measurement]
When high energy is given to an element, almost all elements are in an excited state. When an atom in an excited state returns to a ground state having a low energy level, light specific to the atom is emitted. Inductively coupled plasma (ICP) is argon plasma excited by high frequency induction. The sample sprayed by the nebulizer is introduced into the center of the plasma and excited and emitted. By separating the emitted light according to wavelength by a spectroscope, the type of element is specified from the atomic spectral line. A total emission spectrum from 166 nm to 847 nm can be obtained with a few minutes of measurement. Since the emission intensity at each wavelength is proportional to the number of excited atoms, the concentration of each element can be obtained. By keeping the inside of the spectrometer in a vacuum state, it is possible to analyze elements such as sulfur having an emission spectrum in the vacuum ultraviolet region with high sensitivity, but it is necessary to examine the analysis conditions.

  FIG. 2 shows a schematic diagram of the configuration of the ICP emission analyzer 30. In FIG. 2, reference numeral 31 is an analysis sample solution, 32 is an Ar carrier gas, 33 is an Ar auxiliary nebulizer, 34 is an Ar plasma gas, 35 is a quartz torch, 36 is an induction coil, 37 is Ar plasma, 38 is an emission line, 39 Is a diffraction grating, 40 is a photomultiplier tube (signal output), and 41 is a nitrogen atmosphere. As shown in FIG. 2, the sample of the analysis sample solution 31 (sample introduction system) is introduced into a light source (quartz torch 35 and Ar plasma 37) by an Ar carrier gas 32 and an Ar auxiliary nebulizer 33. Here, the Ar carrier gas 32, the Ar auxiliary nebulizer 33, and the Ar plasma gas 34 constitute a gas supply system. An excitation power supply unit for exciting the Ar plasma gas 34 includes an induction coil 36 and the like. The emission line 38 is condensed by a condensing system (not shown), dispersed by a diffraction grating 39, and detected by a photomultiplier tube (signal output) 40. As shown in FIG. 2, the inside of the spectroscope (diffraction grating 39, photomultiplier tube (signal output) 40) is replaced with an inert gas (nitrogen atmosphere 41). For this reason, it is possible to avoid the problem of sensitivity caused by absorption by air on measurement. Nitrogen is suitable as the inert gas described above, but is not limited thereto. In the ICP emission spectrometer 30 in Example 1, the sulfur component in the extract 31 extracted from the humidifier water is an inductively coupled plasma (ICP) emission analysis method using a spectrometer in which the inside is replaced with an inert gas. It is characterized by measuring and evaluating water quality components.

  FIG. 3 is a block diagram showing the ICP emission analyzer 30 shown in FIG. In FIG. 3, the parts denoted by the same reference numerals as those in FIG. As shown in FIG. 3, the light source unit 21 includes an excitation power source (part) configured by an induction coil 36 and the like, a sample introduction system (sample introduction unit) configured by an analysis sample solution 31, a quartz torch 35, and an Ar plasma. A gas supply system including a light source (light emitting unit) 37, an Ar carrier gas 32, an Ar auxiliary nebulizer 33, and an Ar plasma gas 34 is provided. Subsequently, as shown in FIG. 3, the spectroscopic / photometric unit 22 includes a light collecting line 42 that emits light emitted from the light source unit 21, a spectroscope including a diffraction grating 39, and a photomultiplier tube. A detector composed of (signal output) 40 is provided. The spectroscopic / photometric unit 22 has a nitrogen substitution atmosphere 41 as described above. As shown in FIG. 3, the emission spectrum detected by the spectroscopic / photometric unit 22 is output to the control / calculation / recording unit 23 and amplified by the amplification calculation unit 25 while being appropriately controlled by the control system 24. Recorded in the recording unit 26.

  The above-described ICP emission analyzer 30 is intended for a solution. In particular, the sulfur quantitative analysis line (S = 180.734 nm) is in the vacuum ultraviolet region at an emission line wavelength of 185 nm or less, and the measurement conditions such as nitrogen substitution in the spectrometer were examined. Conditions other than the substitution of nitrogen in the spectroscopic / photometric part 22 of the ICP emission analyzer 30 are set according to conventional methods, and the quantitative analysis method is performed by examining the following main calibration curves for the quantitative analysis elements of sulfur. Established. The apparatus used was Seiko Instruments Inc. (registered trademark) SPS 3100 type.

  In the measurement in the case of performing vacuum ultraviolet analysis (wavelength of 185 nm or less), absorption by oxygen in the air occurs on the short wavelength side of 200 nm or less. In particular, it is strongly absorbed at 185 nm or less. For this reason, in general, when analyzing using a wavelength of 185 nm or less, it is necessary to purge oxygen in the spectroscopic / photometric unit 22 by nitrogen substitution of an inert gas. The method is as follows.

1) A nitrogen purge gas is introduced into the spectroscopic / photometric unit 22 for purging. The purge takes over 2 hours. The gas flow rate is about 10 L / min. Nitrogen gas (99.9 vol% or more, dew point -70 ° C or less).
2) Confirm the stability of the element by nitrogen substitution. The detection limit (DL) of sulfur element to be analyzed in the purge region is measured.
The standard solution was prepared by appropriately diluting a sample amount (NH ₄ ) ₂ SO ₄ : S concentration = 1000 mg / L of a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. and performing matrix matching of the liquid composition. .

The main measurement conditions described above are summarized as follows.
-Sulfur quantitative analysis line: (S = 180.734 nm), for solution.
Standard solution: Sample amount of special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. (NH ₄ ) ₂ SO ₄ : S concentration = 1000 mg / L is appropriately diluted, and matrix matching of the liquid composition is performed.
-The inside of the spectroscopic / photometric unit 22 is replaced with nitrogen. The other conditions were set according to a conventional method.
Apparatus: Seiko Instruments Inc. (registered trademark) SPS 3100 type was used.

FIG. 4 shows the calibration curve relationship between the ICP emission intensity (cpc) (vertical axis) and the S concentration (ppm) (horizontal axis) studied by the inventors under the above measurement conditions. The empirical formula in the calibration curve shown in FIG. 4 is an equation obtained by regression analysis of the obtained straight line, and the S concentration (ppm) = 2.627 × 10 ⁻⁶ χ. Here, χ is ICP emission intensity (cpc). As shown in FIG. 4, correlation coefficient R ² = 0.99991 and lower limit of quantification = 50 ppb.

  Table 1 shows the results of analysis accuracy analysis. As shown in Table 1, when the sulfur concentration is 5.00 ppm, the coefficient of variation after 6 repetitions is 0.91% or less, which is favorable. The analysis accuracy in the industrial water test method (JIS K 0101 method) relating to elemental analysis is generally 2% to 10% in terms of coefficient of variation. Compared to this, it can be seen that the analysis accuracy of this method is good and high, and that the analysis accuracy of the JIS method is sufficiently satisfied.

  As described above, according to Example 1 of the present invention, a humidifier is applied to a polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing a sulfur-based ionic species of an inorganic compound and sulfur of an organic compound component. In the method for measuring sulfur and total sulfur in the measurement of the water quality components of the humidifier water supplied from, the structural material used in the humidifier is an organic film, and the sulfur component in the extract 31 extracted from the humidifier water is used. Measured by inductively coupled plasma (ICP) emission spectrometry using spectroscopic / photometric part 22 whose inside is replaced with inert gas, and carried out a method for measuring sulfur and total sulfur characterized by evaluating water quality components did. Specifically, the sulfur quantitative analysis line (S = 180.734 nm) has an emission line wavelength of 185 nm or less, and the emission line 38 has a short wavelength side of 200 nm or less, because absorption by oxygen in the air occurs during measurement. It was applied to expel oxygen in the spectroscopic / photometric unit 22 by replacing the inert gas with nitrogen gas. By the above, in the measurement by the ICP method of the total sulfur for the humidifier water supplied to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC), the sensitivity problem due to the absorption by the measurement air is avoided. Can provide a method for measuring sulfur and total sulfur. That is, it was possible to establish a micro-quantitative method capable of performing “analysis of total sulfur compounds” composed of inorganic and organic compounds by ICP method at a lower limit of quantification of 1 ppm or less (lower limit of quantification = 50 ppb).

  In Example 2, the water quality component of the water for the humidifier supplied from the humidifier to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC) containing the sulfur type ionic species of the inorganic compound and sulfur of the organic compound component An example using the ion chromatography method 13 will be described as a method for measuring sulfur and total sulfur in the measurement. Here, the structural material used in the humidifier is made of an organic film. First, the ion chromatography method 13 will be described.

[Ion chromatography method 13]
The ion component concentration in the aqueous solution is measured using ion chromatography. The measuring instrument used can measure the concentration of 14 components, including anion and cation components, depending on the equipment conditions. Organic acids (carboxylic acids: -COOH groups are examples), and some other organic acids are analyzed. Is possible.

  5 is a flow chart of ion chromatography in Example 2. FIG. In FIG. 5, reference numeral 61 denotes a liquid feeding unit, 62 denotes a separation unit, 63 denotes a detection unit, and 64 denotes a data processing unit / recording unit. As shown in FIG. 5, a sample is injected (extracted sample) from a sample introduction valve 51 by a pump 65 together with an eluent 52 of weak electrolyte, and passed through a guard column 53 and a separation column 54 made of an ion exchange resin. In the separation column 54, the ion species are separated from each other by the interaction of the hydration radius and the Van der Waals force, and the background conductivity is lowered by passing the removal column (suppressor) 55, and the detection cell 56 and An ion chromatogram (elution time and peak area chart) is measured through the data processor 58. That is, the target ion species is obtained as a chromatogram with high sensitivity. The separation column 54 is generally exchangeable depending on the target ion component.

6 is a schematic diagram of ion chromatography in Example 2. FIG. In FIG. 6, the same reference numerals as those in FIG. In the schematic diagram shown in FIG. 6, a sample containing an ionic component introduced from the sample introduction valve 51 is preliminarily designated with a standard sample solution of a designated component, and the concentration, flow rate, and electrical conductivity of the separation column 54 and the eluent 52 of the apparatus. Consider the separation conditions to be detected in. For sample solution introduction, separation of specified organic ions, SO ₄ ^2- components, etc. will be studied.

  The measurement method in Example 2 is a method in which several types of anion components can be simultaneously measured in one measurement using a sample amount of several μl, and fractional quantitative analysis can be performed. A flow cell type conductivity detector is used as the detection cell (detector) 56. From the peak area and height of the ion chromatogram based on the conductivity of each ion component, the ion component in the target analysis sample solution is detected. The concentration can be determined.

Data processor (analyzer) 58, separation column 54, and eluent 52 were all manufactured by DIONEX (registered trademark). Details are as follows.
Measuring apparatus: ion chromatograph; DIONEX (registered trademark) DX-320, gradient method application type. For main anion / cation analysis [Separation column Ion Pac AS17C, Ion Pac CS14 eluent KOH / EG40 eluent generator used]

As described above, analysis methods for anions / cations and organic acid ions were established by component separation by ion chromatography. FIG. 7 shows an example of an anion chromatogram. In FIG. 7, the vertical axis represents the peak area, and the horizontal axis represents the elution time (min).

  Quantitative analysis is performed by applying a calibration curve to the relationship between the conductivity and concentration of the detected ion species. As described above, it was possible to establish the separation of 14 components by the ion chromatography method 13 for analyzing the anion / cation and organic acid ion. In particular, sulfur-derived sulfate ions can be analyzed.

  As mentioned above, according to Example 2 of this invention, it supplies from a humidifier to the polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing the sulfur type ionic species of an inorganic compound, and sulfur of an organic compound component. In the method for measuring sulfur and total sulfur in the measurement of water quality components in humidifier water, the structural material used in the humidifier is an organic film, and the inorganic compound contained in the structural material in the humidifier water is water-soluble ions The component was extracted with pure water, and the ion species derived from sulfur were simultaneously analyzed and measured by the ion chromatography method 13 to evaluate the water quality component, and a method for measuring sulfur and total sulfur was carried out. Specifically, the sample uses the ionic component of the hollow fiber humidifier module water (humidifier water), the inorganic compound extracts the water-soluble ionic component with pure water, and simultaneously analyzes the ion species derived from sulfur by the ion chromatography method 13 Measured and quantitative analysis of sulfur components. This is to perform quantitative analysis of sulfur components, and to separate and quantitatively analyze ionic species, providing an effect of providing a method for analyzing sulfur-derived polyvalent components such as sulfate ions and sulfite ions. It is done. In addition, the relationship between the peak area consisting of the conductivity of the detected ionic species and the concentration (eg, ppm) is made a calibration curve, and the analysis is performed in the same manner to analyze 14 components other than the sulfur-derived ionic species. You can also As described above, in the measurement by ion chromatography for the humidifier water supplied to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC), the sulfur-derived ionic species of inorganic compounds can be measured accurately and in a short time. It is possible to provide a method for measuring sulfur and total sulfur that can be performed.

  In Example 3, the water quality component of the water for the humidifier supplied from the humidifier to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC) containing the sulfur type ionic species of the inorganic compound and sulfur of the organic compound component An example using gas chromatography / mass spectrometry 14 will be described as a method for measuring sulfur and total sulfur in the measurement. Here, the structural material used in the humidifier is made of an organic film. First, the gas chromatography / mass spectrometry 14 will be described.

[About Gas Chromatography / Mass Spectrometry 14]
FIG. 8 is a schematic diagram of gas chromatography / mass spectrometry 14 (GC / MS). As shown in FIG. 8, a gas chromatography / mass spectrometer (GC / GC) 80 in which a gas chromatography (GC) 80 for separating a volatile mixed sample and a mass spectrometer (MS) 82 are directly connected via an interface 81. MS) is widely used as an analysis method for multi-component trace samples. The molecular weight can be known from the mass number of the molecular ion, and important information regarding the structure of the molecule can be obtained from the fragment ion pattern.

As shown in FIG. 8, the sample entered from the inlet 83 of the gas chromatography (GC) 80 becomes the sample 85 separated by the column 84 and is an ionization chamber (ion) maintained in a high vacuum (10 ⁻⁶ Torr). After being introduced into the source 86), it is successively ionized by electron beam irradiation by the quadrupole electrode 87 or the like. This ion flow is guided to an analysis tube (secondary electron multiplier tube) 88 and separated and detected according to m / z (m: mass number, z: charge) by a magnetic or electric method. What is detected is called a mass spectrum, and is usually shown as a graph consisting of many peaks with the mass-to-charge ratio (m / z) on the horizontal axis and the ionic strength (how much is present) on the vertical axis. .

Analytical conditions for water quality analysis relating to a method for analyzing total sulfur containing organic components are as follows.
(1) Solid Phase Micro Extraction (SPME) method;
A method of concentrating and extracting organic components in water by immersing the fiber with the extraction phase fixed in the sample water.
Sample volume: 10 mL, additive: NaCl 1 g, hydrochloric acid: 1 mol / L 50 μL
(2) GC-MS measurement;
GC-MS measurement was performed with the following apparatus.
Apparatus: GC-MS QP5050A manufactured by Shimadzu Corporation (registered trademark)
Column 84: Capillary column DB-5φ0.25 mm × 30 m, temperature raising condition: 40 to 280 ° C. (10 ° C./min), split ratio: 1/10 (splitless: 1 min), carrier gas: helium (1 mL / min)

  FIG. 9 shows an example of GC-MS analysis TIC (total ion chromatogram of humidifier water). The vertical axis represents ion intensity, and the horizontal axis represents time (min). As shown in FIG. 9, mercaptobenzothiazole, benzothiazole, and the like were detected as sulfur compounds.

  As mentioned above, according to Example 3 of this invention, it supplies from a humidifier to the polymer electrolyte membrane of a solid polymer electrolyte fuel cell (PEFC) containing the sulfur type ionic species of an inorganic compound, and sulfur of an organic compound component. In the measurement method of sulfur and total sulfur in the measurement of water quality components in humidifier water, the structural material used in the humidifier is an organic film, and the organic compound components in the humidifier water are extracted by solid phase microextraction method An organic compound derived from sulfur was measured by gas chromatography / mass spectrometry, and a water quality component was evaluated, and a method for measuring sulfur and total sulfur was carried out. For example, mercaptobenzothiazole, trimethylsilanol, polyphenylsulfone, and the like can be detected as sulfur components from detection and discrimination of many types of components, and the effect of providing an analysis method for organic compound components can be obtained. As described above, in the measurement by ion chromatography for the humidifier water supplied to the polymer electrolyte membrane of the solid polymer electrolyte fuel cell (PEFC), the sulfur-derived ionic species of inorganic compounds can be measured accurately and in a short time. It is possible to provide a method for measuring sulfur and total sulfur that can be performed. Thus, the quantitative analysis of the sulfur component which analyzes and measures the organic component derived from the sulfur which extracted the hollow fiber humidifier module water of the sample with the pure water was established.

  In Example 4, each of the water quality components in the sulfur and total sulfur measurement methods of Examples 1 to 3 is evaluated, and based on these results, the total sulfur is analyzed to evaluate the water quality components. A method for measuring total sulfur was carried out. Specifically, sulfur was measured by the ICP emission analysis method 12, and at the same time, analysis conditions of other elements including pH, conductivity, sulfur-derived ionic components, and components containing heavy metals were examined. Hereinafter, analysis of actual samples will be described with respect to the water quality components of the humidifier water of the solid polymer electrolyte fuel cell (PEFC) according to Example 4.

First, the presence or absence of an eluent that affects the performance of the polymer electrolyte fuel cell (PEFC) is evaluated. The purpose is as follows. Fluororesin ion exchange membranes of polymer electrolyte membranes are currently used. Since these membranes show high H ⁺ ion conductivity only in the wet state, it is necessary to supply moisture to the polymer electrolyte membrane. In order to realize a high-performance solid polymer electrolyte fuel cell (PEFC), establishment of an appropriate water management method for the polymer electrolyte membrane is an important issue.

[Dissolution test method]
In the experiment, pure water is injected from the humidified water inlet and the humidified gas inlet of the humidifier module, and the inlet and outlet are closed and sealed. A 90 ° C. × 50 h test (first time) is performed in a sealed state, and the injected water is sampled, and then the internal pure water is replaced again and the 90 ° C. × 50 h test (second time) is performed again. In this case, a sulfur-based material is used for the structural material film, which becomes humidifier water containing sulfur. As the analysis sample, a part of the sampling amount shown in Table 2 is used. (The A test and B test described below are different film materials).

[Analysis method]
Quantitative analysis was performed on the total sulfur, elution, pH, 14 anions / cations, and 8 metals as elution components. The analysis method was as follows according to the measurement conditions for each element.

The following item 1) is the main body in Example 4, and items 3) and 5) are related important items.
1) Total sulfur (Total-S: TS) by the ICP emission analysis method 12 is measured by introducing vacuum gas into the spectroscopic / photometric unit 22 in a vacuum ultraviolet analysis (wavelength of 185 nm or less).
[Apparatus: ICP emission spectrometer SPS 3100 manufactured by Seiko Instruments Inc. (registered trademark)]
2) Measurement of electric conductivity and pH: Simultaneous measurement of two components at 25 ° C
[Equipment: MM-60R manufactured by Toa DKK Corporation (registered trademark)]
3) Analysis of 14 components of anion, cation and organic acid ion by ion chromatography method 13
[Apparatus: DX-320 manufactured by DIONEX (registered trademark), gradient method application type. For main anion / cation analysis [Separation column Ion Pac AS17C, Ion Pac CS14 eluent KOH / EG40 eluent generator used]
4) Eight component simultaneous analysis of metal components by ICP emission analysis method 12
[Apparatus: ICP emission spectrometer SPS 3100 manufactured by Seiko Instruments Inc. (registered trademark)]
Lower limit of quantification of the above analytical methods: ppb (0.01>), Pb = 0.05>, TS = 0.05
5) Water quality analysis for total sulfur analysis method including organic components
(1) Solid phase microextraction (SPME) method;
(2) GC-MS measurement; GC-MS measurement was performed with the following apparatus.
[Apparatus: GC-MS QP5050A manufactured by Shimadzu Corporation (registered trademark)]

[About the results]
Table 3 shows the results of the quantitative analysis of total sulfur, electrical conductivity, pH, anion / cation component, and metal component (first and second tests) for the inorganic components of the eluted components. FIG. 10 shows the relationship between the main components of SO ₄ ^{2− in} the test (first time) and (second time). FIG. 11 shows the relationship between the main components of total sulfur in the tests (first time) and (second time). 10 and 11, the vertical axis represents the concentration (ppm), and the horizontal axis represents the first and second tests.

[Relationships between main components of the test (first time) and (second time)]
As shown in Table 3 and FIGS. 10 and 11, TS (total sulfur) is derived from a substrate such as SO ₄ ²⁻ and benzothiazole, mercaptobenzothiazole. Ion analysis by the ion chromatography method 13 with a TS quantification lower limit ppb: 0.05>, a metal component quantification lower limit ppb: 0.01>, a Pb quantitation lower limit ppb = 0.05> by the ICP emission analysis method 12. The lower limit of quantification is ppb: 1 ppb.

  The amount of sulfur-based organic substances was large in the B test, and mercaptobenzothiazole was detected at 25.0 mg / L and 19.0 mg / L. Mercaptobenzothiazole is considered to be a vulcanization accelerator. The lower limit of quantification shown for mercaptobenzothiazole is the 0.1 mg / L level.

A test humidifier elution components:
Compared to the first test, the second elution component is the electrical conductivity, pH and main components of the measurement items [Si, SO ₄ ²⁻ , Cl ⁻ , TS (total sulfur), part of heavy metals]. Tend to decrease. Si, SO ₄ ²⁻ , and T—S (total sulfur) have many components derived from the silicon of the structural material, inorganic and organic. In particular, a large amount of Si is thought to lead to precipitation, and the other is considered to cause corrosion.

B test humidifier elution components:
Compared to the first test, the second elution component tends to decrease the electrical conductivity of the measurement items and the main components Si, [SO ₄ ²⁻ , T—S (total sulfur), Si, Cl ⁻ ]. Heavy metal content is particularly low. A particularly large amount of total sulfur is one in which mercaptobenzothiazole is detected at a level of 19 to 25 mg / L. Inorganic ions are considered to be a cause of corrosion. The eluate varies depending on the structural material used in each humidifier. These components are considered to be adsorbed and corroded and become an eluate that affects the battery performance. Example 4 is effective for water quality analysis and evaluation including components such as sulfur.

  As mentioned above, according to Example 4 of this invention, each water quality component evaluation in the measuring method of sulfur of Example 1 thru | or 3 and total sulfur is performed together, Based on these results, total sulfur is analyzed and water quality component evaluation is performed. A method for measuring sulfur and total sulfur was carried out. Specifically, the humidifier material is composed of an organic film as a structural material, and the sulfur component in the extract is measured by ICP emission analysis method 12, and the result including the ionic species containing sulfur of the inorganic compound and the sulfur of the organic compound mass is also obtained. Based on this, total sulfur is analyzed to evaluate water quality, and this is a method for measuring sulfur and total sulfur. In Example 4, an effect is obtained in which sulfur is measured by the ICP emission analysis method 12, and for example, the component concentration is measured by the emission liquid intensity of 180.734 nm in the sample solution. The emission line wavelength of this sulfur (S = 180.734 nm) is in the vacuum ultraviolet region, and measurement conditions such as nitrogen substitution in the spectroscopic / photometric unit 22 are performed. The analytical inspection method can obtain the effect of a quantitative analysis method performed by applying a calibration curve to the relationship between emission intensity and sulfur concentration (eg, ppm). Furthermore, in the ICP emission analysis method 12, other elements as well as sulfur can be obtained by examining the analysis conditions of components including pH, conductivity, ionic components, heavy metals, and evaluation of water quality components of hollow fiber humidifier module water The effect that it can do is also acquired. As described above, the water quality analysis and evaluation method including components such as sulfur eluted in the humidifier water from the polymer electrolyte fuel cell (PEFC) in Example 4 is the sulfur analysis by the ICP emission analysis method 12 and the ion chromatography method. Ion species derived from sulfur of inorganic compounds according to 13 and components according to the form of organic compounds according to gas chromatography / mass spectrometry 14 were established. The humidifier water of the present invention is not limited to the above-described embodiments, and it goes without saying that various modifications may be made without departing from the principle of the present invention.

  FIG. 12 shows a measurement system 90 in the fifth embodiment. Although omitted in FIG. 12, this measurement system 90 also has auxiliary equipment such as reforming equipment, a battery stack, a heat exchanger, a rotating machine, and the like, as in a normal polymer electrolyte fuel cell (PEFC) system. Consists of A fluorine-based cation exchange membrane is used for the polymer electrolyte membrane 100 shown in FIG. 12, and a single cell is configured by sandwiching a joined body of a PEFC anode 98 and a PEFC cathode 99 with a separator (not shown). In this polymer electrolyte fuel cell (PEFC), a gas mainly containing hydrogen supplied from the fuel supply unit 95 is sent to the humidifier 92a together with water supplied from the pure water tank 94, and the humidity is adjusted. After that, it is supplied to the PEFC anode 98. Similarly, the air from the air blowing pump 101 is supplied to the PEFC cathode 99 after the humidity is adjusted through the humidifier 92b. Hydrogen is ionized at the PEFC anode 98 and moves to the PEFC cathode 99 side through the polymer electrolyte membrane 100. On the PEFC cathode 99 side, the hydrogen ions, electrons and oxygen mainly react to generate power, and at the same time, water is generated. The generated water is recovered in the drain water drain tank 96 on the PEFC anode 98 side and the drain water drain tank 97 on the PEFC cathode 99 side, respectively.

  In FIG. 12, reference numerals 92a and 92b are humidifiers that are targets of the measurement methods for evaluating water quality components in the sulfur and total sulfur measurement methods described in Examples 1 to 4, and 91a and 91b are samples used in the measurement method. The collection ports 93a and 93b are flocculated water tanks used in the measurement method. As shown in FIG. 12, in the gas line supplied from the humidifier 92a to the PEFC anode 98 side, the water for the humidifier branches and is collected into the condensed water tank 93a through the sample collection port 91a. Similarly, in the gas line supplied from the humidifier 92b to the PEFC cathode 99 side, the water for the humidifier is branched and collected in the condensed water tank 93b via the sample collection port 91b. In Examples 1 to 4, the humidifier water is collected by sealing the humidifier module, but in Example 5, it is collected from the sample collection port 91a and the like as described above. During normal operation, it is preferable that the sampling ports 91a and 91b are closed and the humidifier water is collected periodically by selecting a time zone in which the amount of power used is small and opening it. The reason is that the humidified gas is discharged from the humidifier 92a and the like, and moisture in the gas is condensed, so that it takes time to collect the sample. As a result, the amount of gas supplied to the solid polymer electrolyte fuel cell (PEFC) decreases, and the power generation efficiency decreases.

  For the humidifier water collected in the condensed water tanks 93a and 93b, the measurement methods for evaluating each water quality component in the method for measuring sulfur and total sulfur described in Examples 1 to 4 are implemented. As a result, in the present measurement system 90, the humidifier water supplied to the polymer electrolyte membrane 100 is appropriately managed, so that a high-performance solid polymer electrolyte fuel cell (PEFC) can be realized. In other words, with respect to the humidifier water extracted from the humidifier 92a and the like, the measurement method of each water quality component evaluation in the sulfur and total sulfur measurement methods described in Examples 1 to 4 is performed, so that The high performance operation of the molecular electrolyte fuel cell (PEFC) can be maintained. That is, a high-performance solid polymer electrolyte fuel cell (PEFC) using water for a humidifier managed by the measurement method of each water quality component evaluation method in the sulfur and total sulfur measurement methods described in Examples 1 to 4 Can be realized.

  As an application example of the present invention, the present invention can be applied to the measurement of sulfur and total sulfur in the measurement of water quality components in humidifier water of a polymer electrolyte fuel cell (PEFC).

11 Water quality component measurement sample, 12 ICP emission analysis method, 13 Ion chromatography method, 14 Gas chromatography / mass spectrometry method, 15
Data organization, 21 light source unit, 22 spectroscopic / photometric unit, 23 control / calculation / recording unit, 24 control system, 25 amplification calculation unit, 26 data recording unit, 30 ICP emission analyzer, 31 analysis sample solution, 32 Ar carrier gas , 33 Ar auxiliary nebulizer, 34 Ar plasma gas, 35 quartz torch, 36 induction coil, 37 Ar plasma, 38 emission line, 39 diffraction grating, 40 photomultiplier tube (signal output), 41 nitrogen atmosphere, 42 condensing system, 51 Sample introduction valve, 52 Eluent, 53 Separation column (guard column), 54 Separation column, 55 Removal column (suppressor), 56 Detection cell, 57 Drain, 58 Data processing device, 61 Liquid feeding unit, 62 Separation unit, 63 detector, 64 data processor / recorder, 65 pump, 80 GC, 81 interface, 8 MS, 83 inlet, 84 column, 85 sample, 86 ion source, 87 quadrupole electrode, 88 secondary electron multiplier, 90 measurement system, 91a, 91b data collection port, 92a, 92b humidifier, 93a, 93b Coagulated water tank, 94 pure tank, 95 fuel supply section, 96, 97 drain water drain tank, 98 PEFC anode, 99 PEFC cathode, 100 polymer electrolyte membrane, 101 pump for air blowing.

JP-A-9-126999 JP 2006-78226 A

"ICP (Inductively Coupled Plasma) emission spectrometer", Tiri News, 2008, vol.027. “Measurement of trace amounts of sulfur / halogen in organic compounds”, Technical News, TN093, 2001-4. Sumika Chemical Analysis Center.

Claims (6)

Sulfur and total in water quality measurement of humidifier water supplied from humidifier to polymer electrolyte membrane of solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of inorganic compound and sulfur of organic compound component A method for measuring sulfur, wherein the structural material used in the humidifier comprises an organic film,
The sulfur component in the extract extracted from the humidifier water is measured by inductively coupled plasma (ICP) emission spectrometry using a spectroscope whose inside is replaced with an inert gas, and the water quality component is evaluated. To measure sulfur and total sulfur. Sulfur and total in water quality measurement of humidifier water supplied from humidifier to polymer electrolyte membrane of solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of inorganic compound and sulfur of organic compound component A method for measuring sulfur, wherein the structural material used in the humidifier comprises an organic film,
The inorganic compound contained in the structural material in the water for humidifiers is characterized by extracting water-soluble ionic components with pure water and simultaneously analyzing and measuring sulfur-derived ionic species by an ion chromatography method to evaluate water quality components. Method for measuring sulfur and total sulfur. Sulfur and total in water quality measurement of humidifier water supplied from humidifier to polymer electrolyte membrane of solid polymer electrolyte fuel cell (PEFC) containing sulfur-based ionic species of inorganic compound and sulfur of organic compound component A method for measuring sulfur, wherein the structural material used in the humidifier comprises an organic film,
Extracting organic compound components in humidifier water by solid-phase microextraction method, measuring organic compounds derived from sulfur by gas chromatography / mass spectrometry, and evaluating water component Measuring method.   Sulfur and total sulfur characterized in that each water quality component in the sulfur and total sulfur measurement method according to claim 1, 2 and 3 is evaluated, and based on these results, total sulfur is analyzed to evaluate water quality components. Measuring method.   A humidifier, a sampling port used for the measurement method, and a flocculated water tank are provided as a target for the measurement method of each water quality component evaluation in the sulfur and total sulfur measurement method according to any one of claims 1 to 4. Measuring system characterized by 5. A solid polymer electrolyte fuel cell characterized by using water for a humidifier controlled by a measuring method for evaluating each water quality component in the method for measuring sulfur and total sulfur according to any one of claims 1 to 4. (PEFC).

Images