JP4755896B2 - Gasoline contamination detector, gasoline contamination detector set, method of using the same, and method of simply using this to determine whether kerosene or light oil meets JIS standards at a gas station - Google Patents

Description

  In the present invention, for example, whether or not gasoline contamination (hereinafter abbreviated as “contamination”) is generated by mixing gasoline in kerosene or light oil. The present invention relates to a gasoline contamination detector capable of estimating the presence or absence of gasoline contamination, a method for using the same, and a method for simply determining whether or not a flash point condition stipulated in the JIS standard is satisfied using the same. .

Gas stations (hereinafter referred to as service stations) sell petroleum products such as gasoline, light oil, and kerosene. Specific examples of these petroleum product supply routes will be described. Petroleum products shipped from a refinery are transferred to tanks in an oil tanker by a tank lorry or a ship. From the oil tank station, tanks are used to supply gasoline, light oil, and kerosene tanks corresponding to each petroleum product at the service station, and then sold to users.
Confirmation of the type of petroleum product is performed at the time of each transfer by checking the written, text, color, etc., and checking the signal with a mechanical key or electric key with a computer, etc. It is intended to prevent mixed oil.
However, the possibility has been reduced by various oil mixture prevention devices. However, in the unloading work, for example, if there is a question that gasoline has been mixed with kerosene or light oil, gasoline contamination has occurred. From the viewpoint of preventing oil accidents, it is necessary to immediately check the properties of petroleum products in the underground tank of the service station.

  When gasoline is mixed into kerosene or light oil and so-called gasoline contamination occurs, the flash point of kerosene or light oil decreases, and in the case of kerosene, a fire due to abnormal combustion of the stove, in the case of light oil, lubrication of the fuel pump of the diesel engine There is a risk of causing defects.

  Conventionally, when a small amount of gasoline is mixed in light oil or kerosene and so-called gasoline contamination occurs, it has been found that measuring the flash point is effective in confirming the amount of mixing. However, in this case, the actual situation is that measurement is not possible on site, and in order to measure the flash point, it must be sent to the testing institution and requested for measurement. It was necessary. In addition, if the amount of gasoline mixed in is large, the flash point will be below normal temperature, and there is a high risk of not only damaging the test equipment but also causing a fire during measurement.

A first object of the present invention is to provide a gasoline contamination detector and a gasoline contamination detection method capable of easily checking whether or not a component having a lower flash point is mixed in kerosene or light oil. .
The second object of the present invention is that when a small amount of gasoline is suspected of being mixed in kerosene or light oil, it is suspected that gasoline has been mixed in kerosene or light oil in order to estimate the mixed amount or flash point. Gasoline contamination detector for detecting whether or not a sample has a flash point easily and quickly, thereby detecting whether or not the sample is contaminated with gasoline, and the degree of sample contamination using the same Provide a method to detect easily, detect whether there is contamination, evaluate whether the kerosene or light oil meets the flash point requirements in JIS standards, and easily detect In the point.

A first aspect of the present invention is a container that can store a sample, a lid or stopper of the container, an air introduction line for supplying air into the sample in the container, and a gas-liquid equilibrium gas existing in the container. suction means for, provided between the suction means and the container, the reaction tube and the reaction tube with replaceable dummy tubes containing reactant which changes color by reaction with vaporized gasoline component of the gas-liquid equilibrium in the gas The present invention relates to a gasoline contamination detector.
The second of the present invention, the suction means, to gasoline contamination detector of claim 1, wherein as it can quantitatively aspirating gas in the system.
According to a third aspect of the present invention, the reaction tube has a vaporized gasoline component concentration in the gas-liquid equilibrium gas of 10 ppm or more, and contains a reactant capable of changing a color changing or coloring region according to the concentration. The present invention relates to a gasoline contamination detector according to item 1 or 2.
A fourth aspect of the present invention is a container that can store a sample, a lid or a stopper of the container, an air introduction line for supplying air into the sample in the container, and a gas-liquid equilibrium gas existing in the container. A reaction tube containing a reactive agent that reacts with the vaporized gasoline component in the vapor-liquid equilibrium gas and is provided between the suction device and the container, a dummy tube replaceable with the reaction tube, and The invention relates to a gasoline contamination detector comprising a judgment table for judging whether or not JIS K 2203 is satisfied when the sample is kerosene and whether JIS K 2204 is satisfied when the sample is light oil .
The fifth aspect of the present invention relates to the gasoline contamination detector according to claim 4, wherein the reaction tube is provided with the same scale as the vertical axis of the judgment table .
A sixth aspect of the present invention uses the gasoline contamination detector according to any one of claims 1 to 3 and firstly attaches a dummy tube, while the sample is put in a container that can store it, and then by a suction means. After sucking the gas in the gas phase part in the container until the gas phase part reaches vapor-liquid equilibrium, air is not allowed to enter the container, and the dummy tube is "reacted containing a reagent that reacts and changes color. Then, the gas in the gas phase in the container that has reached a predetermined amount of vapor-liquid equilibrium is sucked by the suction means, and the part of the scale on the reaction tube is read to see how far the reagent has changed color. The present invention relates to a method for estimating the flash point of a sample by detecting the degree of contamination of the sample from numerical values.
A seventh aspect of the present invention uses the gasoline contamination detector according to any one of claims 1 to 3 and firstly attaches a dummy tube, while the sample is put in a container that can store it, and then by a suction means. After sucking the gas in the gas phase part in the container until the gas phase part reaches vapor-liquid equilibrium, air is not allowed to enter the container, and the dummy tube is "reacted containing a reagent that reacts and changes color. Then, the gas in the gas phase in the container that has reached a predetermined amount of vapor-liquid equilibrium is sucked by the suction means, and the part of the scale of the reaction tube that has changed color is read. When the sample temperature is 25 ° C. , the scale value of the reaction tube is used as it is. When the temperature of the sample in the container is a temperature other than the reference temperature 25 ° C. , the value is used for the reaction tube of the reference temperature 25 ° C. Converted to the scale value, the scale value obtained And Zui relates to a method to estimate the flash point of the sample by detecting the degree of contamination of the sample.
An eighth aspect of the present invention uses the gasoline contamination detector according to any one of claims 1 to 3 and first attaches a dummy tube, while the sample is put in a container that can store it, and then by a suction means. After sucking the gas in the gas phase part in the container until the gas phase part reaches vapor-liquid equilibrium, air is not allowed to enter the container, and the dummy tube is "reacted containing a reagent that reacts and changes color. Then, the gas in the gas phase in the container that has reached a predetermined amount of vapor-liquid equilibrium is sucked by the suction means, and the part of the scale on the reaction tube is read to see how far the reagent has changed color. From the numerical value and the temperature of the sample in the container at the time of measurement, using kerosene judgment table in the case of kerosene , using kerosene judgment table in the case of light oil, the kerosene or light oil to be measured is each JIS K 2203 or JI Whether conditions are satisfied or flash point K 2204 relates to a method for judgment.
A ninth aspect of the present invention uses the gasoline contamination detector according to claim 4 or 5 and first attaches a dummy tube, while the sample is put in a container that can accommodate it, and then the gas phase is sucked by a suction means. After sucking the gas in the gas phase part in the container until the part reaches vapor-liquid equilibrium, air is not allowed to enter the container, and the dummy tube is "reactor tube containing a reagent that reacts and changes color". Then, the gas in the gas phase part in the container that has reached a predetermined amount of gas-liquid equilibrium is sucked by the suction means, and in the case of kerosene , the light oil is placed at the position corresponding to the temperature of the sample in the container in the kerosene judgment table . In this case, the reaction tube is placed parallel to the scale axis of the reaction tube at the position corresponding to the temperature of the sample in the container in the determination table for light oil, and the boundary position between the portion where the reagent in the reaction tube is discolored and the portion where the color is not discolored , in the case of kerosene-size for kerosene Or in the region of "no problem" in the table, the "necessary measures" or in the region of, or read what is in the region of the "off-specification", also in the case of light oil "no problem" in the light oil determination table By reading whether it is in the area, “measurement required” area, or “non-standard” area, the kerosene or light oil that is the object of measurement is JIS K 2203 or JIS K 2204 , respectively . whether or not the conditions are met in the flash point relates to a method of judgment.

  The reactant used in the present invention is a compound that changes color or develops color when it comes in contact with light hydrocarbon gas, which is a vaporized component of gasoline, such as chromium oxide (reduction reaction) that changes from orange to black-green by hydrocarbon gas. Use.

The reaction tube of the present invention, the are those reactants was filled with, although the gas-liquid concentration vaporized gasoline component is more than 10ppm equilibrium gas (usually in concentrations ranging from 10ppm~3 volume%, the gasoline components Reagents that change color according to the size of the product, such as chromium oxide, can be used regardless of how high the concentration is, for example, a commercial product filled with chromium oxide (this product has a subtle degree of discoloration at a concentration between 10 ppm and 3% by volume). 101) or 101L manufactured by Gastec Co., Ltd. can be used. Since the reactant has a high reactivity with the vaporized gasoline component, it reacts sequentially from the reactant that initiates contact with the vaporized gasoline component according to the concentration of the vaporized gasoline component. Corresponding to the color change or coloring region of the reactant, the reaction tube 7 in FIG. The commercial product is a reaction tube made of glass, and the unused product is vacuumed to prevent discoloration of the reactants therein, and the glass at both ends is melt-sealed. One is connected to a vinyl pipe connected to the gas-liquid equilibrium gas supply pipe, and the other is connected to a vinyl pipe connected to the absorbing means.

  As a container which can store the sample used in the present invention, a container having a volume of about 10 to 1000 ml, preferably 20 to 500 ml, particularly preferably 50 to 300 ml is used. Although there is no restriction | limiting in particular in the material which comprises a container with such a capacity | capacitance, For example, a glass bottle etc. can be used.

  It is preferable that the amount of the sample put in the container is an amount occupying about 1/4 to 4/5, preferably about 1/3 to 2/3 of the container. This amount can perform the test stably and without mistakes.

  The suction means used in the present invention preferably has a function capable of quantitatively sucking the gas in the system. Such suction means include a manual suction pump, a suction pump with a flow meter, and the like, but means that does not use electricity to handle dangerous substances is preferable. The absorption pump is preferably of the type having a check valve. A cock is preferably provided between the suction means and the reaction tube or dummy tube. It is also preferable to provide a cock between the gas-liquid equilibrium gas supply pipe and the reaction tube or dummy tube. However, even without these cocks, there is almost no possibility that air will enter the container and break the vapor-liquid equilibrium in the container.

  The suction amount can be 0.2 to 5 times, preferably 0.5 to 2 times the volume of the gas volume in the container.

  Usually, the concentration of the hydrocarbon gas (vaporized gasoline component) in the gas containing the vaporized gas of gasoline is approximately 20 to 35% by volume, although it varies depending on the temperature and the type of gasoline. On the other hand, the hydrocarbon concentration in the gas containing the vaporized gas of kerosene and light oil is extremely low, and the hydrocarbon concentration is 0.05 to 0.09% by volume in the case of kerosene, and is 0.00 in the case of light oil. 05% by volume or less. In the present invention, when a small amount of gasoline is mixed in light oil or kerosene, the mixture of gasoline is detected by utilizing the fact that the hydrocarbon concentration in the gas containing the vaporized gas is remarkably increased.

A specific example of the present invention will be described with reference to FIG. 1 is a glass bottle, 2 is a rubber stopper, 3 is an air introduction pipe, 4 is a sample (liquid), 5 is a gas phase (gas), 6 is a gas-liquid equilibrium gas supply pipe (L-shaped tube), and 7 is a reaction. A tube (with a scale) 8 is a suction means, and the reaction tube 7 is detachably attached between the gas-liquid equilibrium gas supply pipe 6 and the suction means 8. A defroster stone may be attached to the liquid end of the air introduction pipe. The diffuser stone is a device for reducing the bubble size in the liquid of the air introduced, and can achieve the vapor-liquid equilibrium state of the gas phase portion in the container more reliably. Further, it is preferable to provide a means for measuring the liquid temperature of the sample 4. The simplest means is a method of inserting a thermometer into the air introduction pipe, but is not limited to this. Also, various types of thermometers can be used.
The gasoline contamination detector used in the following examples and comparative examples has a glass bottle 1 with a volume of 200 ml, a sample (liquid) contained therein of 100 ml, a gas phase (gas) of 100 ml, and a suction means 8 at a stroke. Although 100 ml can be aspirated, it can be aspirated in 50 ml portions, and one aspiration in [0015] is 50 ml. The reaction tube 7 used was 101 manufactured by Gastec Corporation, which has an inner diameter of about 3 mm, an outer diameter of about 5 mm, a total length of about 13 cm, and a length of the reactant-filled portion of about 5 cm.

As an example of a specific method of using the apparatus shown in FIG. 1, first, the reaction tube 7 is removed, and a dummy tube, for example, a used reaction tube or a simple glass tube not filled with a reactant is installed instead of the reaction tube 7. After that, half of the volume of the gas phase 5 is sucked in twice using the suction means (the number of times of suction is two times). By this suction, air outside the system is introduced into the sample 4 in the glass bottle 1 through the air introduction pipe, and the sample is bubbled. By this bubbling, the gas phase 5 in the glass bottle 1 is filled with a gas-liquid equilibrium gas.
At this stage, the dummy tube is removed so that the gas-liquid equilibrated gas in the glass bottle 1 does not leak, the reaction tube is attached, and the half of the volume of the gas phase 5 is once again sucked by the suction means (the number of times of suction is This is the third time). After the suction is completed, the scale value of the reaction tube is read, and the amount of gasoline mixed in the sample is estimated from the scale value. In order to prevent the gas-liquid equilibrium gas in the glass bottle 1 from leaking, an air inflow blocking means such as an openable / closable cock is attached to or near the end of the gas-liquid equilibrium gas supply pipe. The glass tube and the reaction tube 7 may be exchanged while the air inflow prevention means is closed, and the air inflow prevention means such as the cock may be in the open state after completion of the exchange. Good.
FIG. 9 shows that a test sample (1.0% by volume gasoline-contaminated kerosene) is put in a container, the reaction tube 7 is replaced corresponding to each suction frequency, and the scale value of the reaction tube 7 corresponding to each suction frequency is read. This is a graph. As can be seen from FIG. 9, when half the volume of the gas phase in the container is sucked, it can be understood that gas-liquid equilibrium has been achieved since the third suction. In other words, if the entire volume of the gas phase is sucked once, the subsequent gas phase can be regarded as having achieved a gas-liquid equilibrium.

A method for converting the scale value of the reaction tube to the scale value of the reaction tube at the reference temperature when the measurement temperature is a temperature other than the reference temperature will be described below by taking the case where the reference temperature is 25 ° C. as an example.
As a formula for estimating the flash point of kerosene or light oil mixed with gasoline from the scale of the reaction tube, the following formula ( 1 ) or formula ( 2 ) can be cited as a simple formula. The calculation methods used are shown in Examples 1 to 6 and Comparative Examples 1 to 4. However, this formula ( 1 ) and formula ( 2 ) are applicable only when the measurement temperature (liquid temperature) is 25 ° C.
Therefore, in a common sense environment where a normal service station is installed, the flash point of kerosene or light oil mixed with gasoline can be estimated from the scale of the reaction tube under any environmental conditions. A method for converting the measured sample temperature into data when measurement is performed at a sample temperature of 25 ° C. will be described below. When the measurement temperature is 25 ° C., only the scale of the reaction tube is seen. When the measurement temperature is other than 25 ° C., the scale of the reaction tube at the measurement temperature is converted to the scale value of the reaction tube. The sample quality can be judged simply and quickly. This case is shown in Examples 7 and 8.

(1) When the sample is kerosene,
Method for converting from the scale value at the sample temperature when actually measured to the scale value at the sample temperature of 25 ° C.
Note that α is the same sample, but only the temperature is different, but the same experiment was conducted under the other conditions, and the results (measured temperature and measured scale value at the measured temperature) measured in the reaction tube were measured. It is a constant obtained by approximating an exponential function with respect to temperature, and e is the base of the natural logarithm. The constant for a sample with an arbitrary amount of contamination can be calculated by the complement method using the constants obtained for samples with a known amount of contamination. Incidentally, in Example 7, 0.026, which is the average value of the index calculated from the approximate expression of the exponential function in the case of 0.5% and 1.0% gasoline contamination in Table 10, was used for simplification.
(2) When the sample is light oil,
A method for converting the scale value at the sample temperature when actually measured into the scale value when measured at the sample temperature of 25 ° C. is as follows.
Note that β is the same sample, but only the temperature is different, but the other conditions are the same, and the results (measured temperature and measured scale value at the measured temperature) measured in the reaction tube were measured. It is a constant obtained by approximating an exponential function with respect to temperature, and e is the base of the natural logarithm. The constant for a sample with an arbitrary amount of contamination can be calculated by the complement method using the constants obtained for samples with a known amount of contamination. Incidentally, in Example 8, 0.024, which is the average value of the exponents calculated from the approximate expression of the exponential function in the case of 0.5% and 1.0% gasoline contamination in Table 11, is used for simplification.

(A) Satisfies JIS standard as kerosene or light oil even if it is contaminated if the reaction tube scale value at 25 ° C. is below (safe for handling as kerosene or light oil), (B) It is in the gray zone whether the scale value of the reaction tube at 25 ° C meets the JIS standard as kerosene or light oil (it is in a delicate area of safety or danger when handled as kerosene or light oil, In other words, it is delicate whether or not each JIS standard is satisfied, and analysis by an appropriate inspection organization is necessary.) (C) If the scale value of the reaction tube at 25 ° C is greater than or equal to that of kerosene or light oil (A), (B), (C) cases where it may be judged that the product does not meet the JIS standards (it is dangerous to handle as kerosene) I superimposed a number of experiments.
Based on the scale value of the reaction tube and the flash point data obtained by measuring the light hydrocarbon content in the gas-liquid equilibrium gas in the gas phase in the reaction tube at 25 ° C. (component caused by gasoline contamination), the minimum 2 A highly correlated linear function was derived by multiplication. The specific method is shown in the figure. FIG. 10 shows the case of kerosene, and FIG. 11 shows the case of light oil.
In addition, in the case of kerosene and light oil, the relationship between the flash point and the scale value can be expressed by a linear function as shown by the equations in FIGS. 10 and 11 (where y is the vertical axis, x Is the horizontal axis). In such a case, if one numerical value is known, the other numerical value can be predicted. The statistic R indicating the strength of the relationship between the two values at this time is 0.955 in the case of FIG. 10 and 0.959 in the case of FIG. 11. From this value, the flash point and the scale value are It can be seen that there is a very high correlation. From this, the inventions of claims 4, 5 and 9 were born. The scale of the reaction tube corresponds to the volume% of the gasoline component in the gas phase.

  According to JIS standards, the flash point of kerosene is determined to be 40 ° C. or higher, and the flash point of light oil is determined to be 50 ° C. or higher. With this in mind, it was judged appropriate to apply the following criteria.

<In the case of kerosene>
(A-1) When the scale value of the reaction tube at 25 ° C. is less than 0.17, there is no danger of gasoline contamination, and it satisfies the flash point condition (40 ° C. or higher) in JIS standard as kerosene. It may be interpreted as a “no problem” area.
(B-1) When the scale value of the reaction tube at 25 ° C. is 0.17 to 0.36, there is a risk of gasoline contamination, so the flash point of the JIS standard as kerosene by the test engine It is necessary to measure whether the conditions are satisfied (measurement required).
(C-1) If the scale of the reaction tube at 25 ° C exceeds 0.36, there is a risk of gasoline contamination, and it does not meet the flash point conditions in the JIS standard for kerosene (nonstandard )

<For light oil>
(A-2) When the scale value of the reaction tube at 25 ° C. is less than 0.23, there is no danger due to gasoline contamination, and it may be interpreted as a “no problem” area that satisfies the JIS standard as light oil. .
(B-2) If the scale value of the reaction tube at 25 ° C is 0.23 to 0.31, there is a risk of gasoline contamination, so the flash point of the JIS standard as light oil by the test engine It is necessary to measure whether the conditions are satisfied (measurement required).
(C-2) If the scale value of the reaction tube at 25 ° C exceeds 0.31, there is a risk of gasoline contamination, and it does not satisfy the flash point conditions in the JIS standard as light oil (non-standard )

The determinations in (A), (B), and (C) are based on the scale value of the reaction tube at 25 ° C., but the reactant in the reaction tube senses light hydrocarbons. Therefore, since the vapor pressure of hydrocarbons increases as the measurement temperature increases, there is a temperature dependency that the scale value of the reaction tube naturally increases. In other words, the scale value of the reaction tube decreases as the temperature decreases.
Therefore, a judgment standard using measurement results at various temperatures other than the standard temperature is necessary.

Therefore, it is preferable to create a relationship diagram between the measured temperature and the scale value of the reaction tube, that is, a determination diagram for safety or danger.
To that end, samples of kerosene and diesel oil with gasoline contamination of 0.00%, 0.25%, 0.50%, 0.75%, and 1.00% (both are volume%) are prepared, and the sample temperature The scale value of the reaction tube at 5 ° C, 15 ° C, 25 ° C and 30 ° C was determined.
The results are as shown in the table below.

  FIG. 12 and FIG. 13 are graphed using Table 1 and Table 2.

As described above, it is very important how many times the temperature at the time of measurement of a sample of kerosene or light oil to be used for measurement is measured. If kerosene or light oil stored in a tank is collected, brought indoors, and measured indoors, the sample temperature at the time of collection and the actual measurement temperature will not match in most cases. Therefore, it is preferable to leave the sample at the time of measurement in the measurement chamber for a predetermined time.
By the way, when 100 ml of kerosene and light oil are put in the glass bottle (diameter 55 mm, volume 200 ml) used in Examples 1 to 8 described later, a thermometer is inserted in the central part of the glass bottle and left in a room at 25 ° C. When the time until the liquid temperature reached 25 ° C. was examined, it was as follows.
Temperature at the time of collection Time until the liquid temperature equilibrates with room temperature
0 ° C 47 minutes
5 ° C. 44 minutes 10 ° C. 40 minutes 15 ° C. 33 minutes 20 ° C. 22 minutes Therefore, it is preferable to perform the measurement in consideration of the temperature at the time of collection.
When measuring in the field, if the measurement is performed after being collected in a glass bottle and left in the measurement chamber for 1 hour, the room temperature may be considered as the temperature of the sample.

Claim 4,5, the invention of 8 and 9, that take advantage of the graduated corresponding to the vertical axis of the graph of FIG. 14 or FIG. 15 is a safe or dangerous or judgment table reaction tube. FIG. 14 is a graph showing selection of curves passing through reaction tube scale values of 0.17 and 0.36 at 25 ° C. in FIG. 12, and FIG. Curves passing through 23 and 0.31 are selected and illustrated respectively. When the sample is kerosene, the display board displaying the graph of FIG. 14 which is a determination table for kerosene is used, and when the sample is light oil, the display board displaying the graph of FIG. 15 which is a determination table for light oil is used. The scale of the reaction tube corresponding to the vertical axis of the display plate is the same for both the graph of FIG. 14 and the graph of FIG. 15, so the scale of the reaction tube is the same for both kerosene and light oil. is there.
Since the horizontal axis of the graph of FIG. 14 or 15 is the temperature of the sample in the container, the reaction tube is positioned at the corresponding temperature on the horizontal axis of the display panel displaying the graph of FIG. 14 or FIG. if set to 14 or 0.00 position of the display panel that displays the graph of FIG. 15 the zero point of the scale of the reaction tube, "no problem" test samples, also namely the above the flash point of the JIS standard It may be below the flash point of JIS standard due to “measurement required”, that is, gasoline contamination, and it is necessary to measure the flash point at the test engine, or “out of standard”, that is, JIS standard because of gasoline contamination. It can be immediately determined whether it is below the flash point.

  The display board may be (i) a gasoline contamination detector and the display board are separate, or (b) a gasoline contamination detector.

When the gasoline contamination detector of (a) and the display plate are separate, the gasoline contamination detector according to any one of claims 1 to 3 is used, and the reaction tube is replaced with a dummy tube, while the sample is Put it in a container that can store it, and then suck the gas in the gas phase part in the container until the gas phase part reaches gas-liquid equilibrium by suction means, so that air does not enter the container Then, replace the dummy tube with a “reactor-containing reaction tube”, and after sucking the gas in the gas phase in the container that has reached a predetermined amount of gas-liquid equilibrium with the suction means, remove the reaction tube from the gasoline contamination detector. Separately, for example, the scale of the reaction tube is used as the vertical axis of the “display plate” prepared on the desk, and the discoloration position of the reaction tube is “no problem” on the display plate displaying the graph of FIG. In the area of Or in the region of the main measurement ", or in the region of" non-standard ", read the.

When the gasoline contamination detector (b) and the display plate are integrated, they may be handled, for example, as shown in FIG. The integration method is not particularly limited, but is preferably a detachable method.
FIG. 16 shows a specific example in the case where the display board is used by being attached to a gasoline contamination detector. This example shows an example in which it is difficult to provide a scale on the reaction tube itself, and the reaction tube 7 and the scale plate are integrated as the reaction tube 7. Of course, when the reaction tube itself is calibrated, the reaction tube itself may be graduated. [Note that these points can be said in both cases (b) and (b)). Since the display board 9 in FIG. 16 corresponds to FIG. 14, in this case, it is used for inspection of gasoline contamination kerosene. In addition, it is preferable to use a transparent synthetic resin board for the said scale board in the case where a display board is integrally attached to a gasoline contamination detector as shown in FIG.

Further, in the gasoline contamination detector set of FIG. 16, the reaction tube is arranged such that the reaction tube is arranged at the position of the vertical axis corresponding to the temperature of the sample in the container on the display board displaying the graphs of FIGS. As means for adjusting the positional relationship between the display panel and the display panel, the display panel may be moved in the horizontal direction, or the reaction tube may be moved in the horizontal direction.

The gasoline contamination detector according to the present invention can be stored in a trunk with a sponge cushion, for example, as shown in the photograph of FIG.
The gasoline contamination detector of FIG. 17 is a case where the thing of FIG. 1 is accommodated in the trunk.

(1) According to the present invention, when there is a concern that a small amount of gasoline is mixed with light oil or kerosene, the level of this contamination is measured at the site easily and in a very short time. The degree of influence can be estimated and the response can be taken immediately.
As a result, it is possible to prevent a product whose flash point is out of specification from being sold by mistake.
(2) According to the present invention, when the measurement temperature is a reference temperature (for example, 25 ° C.), only the scale of the reaction tube is seen, and when the measurement temperature is other than the reference temperature (for example, 25 ° C.), the measurement temperature By simply converting the scale value of the reaction tube to the scale value of the reaction tube at the reference temperature (for example, 25 ° C.), it is possible to easily and quickly determine the suitability of the sample.
(3) In particular, according to the invention of claim 9 using the gasoline contamination detector set of claim 4 or 5, when the liquid temperature at the time of measurement and the scale value of the reaction tube are kerosene, the graph of FIG. Since the scale of the vertical axis corresponds to the scale of the vertical axis of the graph of FIG. 15 in the case of light oil, it responds to the position of the vertical axis of the display board displaying the graph of FIG. 14 or FIG. 15 as a judgment table . If the tube is attached and the discoloration position of the reaction tube is within the “no problem” range on the display panel, it can be immediately determined that the flash point satisfies the JIS standard, and if it is within the “out of standard” range. It can be immediately determined that the flash point does not satisfy the JIS standard. If the display board is within the “measurement required” range, it cannot be quickly stopped, and the analysis is requested from an appropriate testing institution.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by these examples. In addition, since the invention of Claims 4, 5, and 9 is sufficient in the above description, the Example is not provided. FIG. 16 can be said to be one embodiment.

Experimental example (1) Relationship between the amount of gasoline contamination and the flash point The relationship between the amount of gasoline contamination and the flash point when gasoline was mixed in kerosene or light oil was determined by experiments. This flash point is determined according to JIS K 2265. The relationship between the gasoline contamination amount and the flash point when gasoline is mixed in kerosene is shown in Table 3 and FIG. 2, and the relationship between the gasoline contamination amount and the flash point when gasoline is mixed in light oil is shown in Table 4 and FIG. The gasoline used in this experimental example is JIS K 2202, No. 2 regular gasoline, kerosene is JIS K 2203, No. 1 kerosene, and light oil is JIS K 2204, No. 1 diesel oil. When Table 1 and Table 3 or Table 2 and Table 4 are compared, the flash point is slightly different even if the gasoline contamination is the same, but this is different from the experiments in Table 1 and Table 3 or Table 2 and Table 4. This is because the gasoline, kerosene or light oil used was not from the same lot. The present invention provides an apparatus and a method that can be used satisfactorily even if there is such a difference between lots.

(2) Relationship Between Gasoline Contamination Amount and Reaction Tube Scale Value The relationship between the gasoline contamination amount and the reaction tube scale value is shown in Table 5 and FIG.

(3) Relation between reaction tube scale value of kerosene or light oil mixed with gasoline and estimated flash point Based on Tables 3 and 5 with the amount of gasoline contamination as a parameter, kerosene mixed with reaction tube scale value and gasoline The estimated flash point is indicated by a solid line in FIG. Similarly, based on Tables 4 and 5, the reaction tube scale value and the estimated flash point of light oil mixed with gasoline are shown by solid lines in FIG.
A black square mark in FIG. 5 indicates a flash point based on JIS K 2265 of kerosene, and a black square mark in FIG. 6 indicates a flash point based on JIS K 2265 of light oil. Also, the solid lines in FIGS. 5 and 6 are obtained by linearly approximating numbers corresponding to the respective black square marks, and are displayed as the following formulas (3) and (4), respectively.

Each coefficient is obtained from the intercept and inclination of the flash point axis. In this example, A ₁ = 4, B ₁ = 43, A ₂ = 3, and B ₂ = 80. The number may vary depending on the type.

The reaction tubes and suction devices used in Examples 1 to 8 and Comparative Examples 1 to 4 are as described below.
Reaction tube (product name, detection tube): 101 manufactured by GASTEC (conforms to JIS K 0804)
Suction device: Gas sampling device manufactured by GASTECH Sample volume: 100ml Suction volume: 50ml
* Oil temperature during measurement is about 25 ° C
[Preparation before measurement (sample preparation, gas replacement)]
(1) Pour the sample into the marked line in the center of the glass bottle 1 shown in FIG.
00 ml).
(2) Close the stopper 2 (tightly).
As shown in the figure, (3) Flexibility attached to the gas-liquid equilibrium gas supply pipe of L-shape (only the L-shape portion is preferably made of a flexible material such as rubber). Attach one of the dummy tubes to the end of the sex tube. The dummy tube is convenient and economical to use a reaction tube that has already been measured.
(4) Attach a suction means to the other side of the dummy tube and suck 100 ml. Keep it bubbling until it's finished (about 1 and a half minutes).
(Adjust the suction means to the 100 ml scale and pull until you hear a click.)
(5) Remove the dummy tube.
[Measurement]
(6) Fold both ends of the reaction tube, attach one to the flexible tube and the other to the suction means,
Aspirate 50ml by pulling to 0ml until it clicks. Keep it until bubbling is complete (approximately 50 seconds).
(7) Remove the reaction tube and read the scale value.
(8) Remove the stopper and measure the sample temperature.
(9) A correction value is calculated from the read scale value and sample temperature according to the equations (1) to (4).

Examples 1-2
Measured by mixing a small amount of gasoline with light oil. The oil temperature at the time of measurement is about 25 ° C.
The estimated gasoline mixture amount was calculated from the reading of the reaction tube in FIG.
Found gasoline mixed amount are those determined by C ₅ or less fractions of the gas chromatographic analysis method specified in JIS K 2536, the estimated gasoline mixed amount is a value obtained from the reaction tube scale with reference to FIG.

Examples 3-6
Measured by mixing a certain amount (0, 0.5, 1, 2%) of gasoline with light oil.
From the reading of the reaction tube, the estimated gasoline mixture amount was obtained using FIG. 4, and the estimated flash point was obtained using Equation (4) of Equation 3.
The measured flash point was measured using a Pensky-Martens flash point tester in samples 3 to 5, and a tag sealed flash point tester in sample 6 (because the flash point was estimated to be quite low), Both are compliant with JIS K 2265.
In sample 6, there is a considerable difference between the estimated flash point and the measured flash point, but this seems to have occurred because the flash point test method is different.

Comparative Examples 1-2
Measurement was performed using samples 4 and 5 without aspirating 100 ml before measurement and without achieving vapor-liquid equilibrium.
From the scale value of the reaction tube, the estimated gasoline mixture amount was obtained using FIG. 4, and the estimated flash point was obtained using Equation (4) of Equation 3.
The measured flash point was a Pensky-Martens flash point tester in Comparative Example 1 and a tag-sealed flash point tester (because the flash point was estimated to be quite low) in Comparative Example 2, and Example 3 Measured in the same manner as ˜6.
Since the vapor-liquid equilibrium is not achieved, the scale value of the reaction tube is lowered. As a result, the flash point is calculated to be high while the gasoline mixing amount is low.

Comparative Examples 3-4
Measurement was performed using Sample 5 and Sample 6 without sealing the container opening (without using the rubber stopper in FIG. 1).
From the reading of the reaction tube, the estimated gasoline mixture amount was obtained using FIG. 4, and the estimated flash point was obtained using Equation (4) of Equation 3.
In the comparative example 3, the measured flash point was measured using a Pensky-Martens flash point tester, and in the comparative example 4, a tag sealed flash point tester (because the flash point was estimated to be considerably low). It was measured similarly to 6.
Since the air in the outside air is also introduced into the reaction tube, the scale value of the reaction tube is further lower than those of Comparative Examples 1 and 2. Therefore, the flash point is calculated to be higher while the gasoline mixing amount is lower.

Example 7
Relation between scale value of reaction tube using kerosene sample and measurement temperature In order to investigate how the scale value of reaction tube changes with respect to sample temperature when measuring the contamination by gasoline, different gasoline contamination Four types of kerosene samples (0.0%, 0.5%, 1.0%, 1.5%) are prepared, and under four temperature conditions (5 ° C, 15 ° C, 25 ° C, 30 ° C) Then, when the contamination by gasoline was measured by the gasoline contamination detector of the present invention, the scale value of the reaction tube was as shown in the following table. In addition, flash points according to JIS K 2265 were separately obtained and listed in the table for reference.
Using the data in Table 10, the scale value of the reaction tube at a measurement temperature of 25 ° C. and JIS K
The relationship with the flash point of 2265 is shown in FIG. When the flash point of JIS K 2265 is 40 ° C. (standard value of kerosene of JIS K 2203), the scale value of the reaction tube is 0.28 when estimated from FIG.
Further, the relationship between each measured temperature and the scale value of the reaction tube can be approximated by an exponential function. For example, when the gasoline contamination amount is 0.5% and 1.0%, the equations (5) and (6) are used. Is displayed.
For the sake of simplification, “reaction tube scale value at each measurement temperature” is converted to “reaction tube scale value at 25 ° C.” using 0.026 which is the average value of the indexes of the above formulas (5) and (6). The method to do is displayed by the following formula.
From the above points,
When the sample is kerosene, the scale value (the value when the measured temperature is 25 ° C., the converted value using the formula (1 ′) when the temperature is other than that) is less than 0.28. In view of this, it is considered that the flash point of the JIS K 2203 flash point satisfies the standard value of 40 ° C. or higher. However, considering that the error of the reaction tube is stipulated by JIS K 0804 as an indication accuracy of ± 35% or less and that the flash point of kerosene has a slight range, the flash point is estimated to be about 5 ° C higher. The scale value (0.15) to be used is used as a judgment criterion for contamination by gasoline.
According to this standard, when the scale value (including the conversion value) of the reaction tube of the gasoline contamination detector is 0.15 or less: There is no substantial contamination. The flash point is estimated to be 40 ° C or higher.
The flash point conditions as kerosene of JIS K 2203
Judge that you are satisfied.
If it exceeds 0.15: Contamination is considered, according to JIS K 2265
It is necessary to check the flash point.
It can be judged.

Example 8
Relationship between reaction tube scale value and measurement temperature using a light oil sample different from Examples 1 to 6 How the scale value of the reaction tube changes with respect to the sample temperature when measuring contamination from gasoline 4 types (0.0%, 0.5%, 1.0%, 1.5%) of light oil samples with different gasoline contamination levels were prepared, and four temperature conditions (5 ° C, 15 ° C) were prepared. , 25 ° C., 30 ° C.) When the gasoline contamination detector of the present invention was used to measure the contamination by gasoline, the scale values of the reaction tubes were as shown in the following table. In addition, flash points according to JIS K 2265 were separately obtained and listed in the table for reference.
Using the data in Table 11, the scale value of the reaction tube at the measurement temperature of 25 ° C. and JIS
FIG. 8 shows the relationship between the flash point of K2265. When the flash point of JIS K 2265 is 50 ° C. (standard value of light oil of JIS K 2204), the scale value of the reaction tube is estimated to be 0.36 from FIG.
Further, the relationship between the temperature at the time of each measurement and the scale value of the reaction tube can be approximated by an exponential function. For example, in the case of gasoline contamination amounts of 0.5% and 1.0%, equations (7) and (8 ) Is displayed.
For simplification, “reaction tube scale value at each measurement temperature” is converted to “reaction tube scale value at 25 ° C.” using 0.024 which is the average value of the indexes of the above formulas (7) and (8). The method to do is displayed by the following formula.
From the above points,
When the sample is light oil, the scale value (the value when the measurement temperature is 25 ° C., the conversion value using the formula (2 ′) at other temperatures) is less than 0.36. From the viewpoint of No. 8, it is considered that the standard value of flash point of light oil of JIS K 2204 is 50 ° C. or more. However, considering that the error of the reaction tube is specified as JIS K 0804 with an indication accuracy of ± 35% or less, and that the flash point of light oil has a slight range, the flash point is estimated to be about 10 ° C higher. The scale value (0.20) to be used is used as a judgment criterion for contamination by gasoline.
According to this standard, when the scale value (including the conversion value) of the reaction tube of the gasoline contamination detector is 0.2 or less: there is no substantial contamination. The flash point is estimated to be 50 ° C or higher.
JIS K 2204 diesel oil (Special No. 1, No. 1,
It can be judged that the flash point condition as No. 2) is satisfied.
If it exceeds 0.2: It is considered that there is contamination, according to JIS K 2265
It is necessary to check the flash point.
It can be judged.
Since the present invention is characterized by the fact that it is possible to substantially determine the presence or absence of contamination without examining the flash point of JIS each time a sample is inspected. Is determined by converting the scale value of the reaction tube at the temperature at the time of each measurement into a scale value of 25 ° C. (no conversion is necessary when the sample temperature is 25 ° C.) without examining the JIS flash point. (The same applies to Example 7).

One specific example of the gasoline contamination detector of the present invention is shown. The relationship between the amount of gasoline contamination and the flash point when gasoline is mixed into kerosene is shown. The relationship between the amount of gasoline contamination and the flash point when gasoline is mixed in light oil is shown. The relationship between the amount of gasoline contamination and the reaction tube scale value is shown. The relationship between the kerosene flash point estimated value mixed with gasoline and the reaction tube scale value is shown. The relationship between the estimated flash point of light oil mixed with gasoline and the scale value of the reaction tube is shown. The relationship between the reaction tube scale value of kerosene mixed with gasoline at 25 ° C. and the JIS flash point is shown. The relationship between the scale value of the reaction tube at 25 ° C. and the JIS flash point of light oil mixed with gasoline is shown. Put the test liquid (kerosene contaminated with 1.0% by volume of gasoline) into the container, replace the reaction tube according to the number of suctions, and read the scale value of the reaction tube corresponding to the number of suctions. It is a thing. Contaminated kerosene mixed with kerosene in the range of 0 to 1.0% is applied to the gasoline contamination detector shown in FIG. 1 used in the example, and the scale value is examined, and the flash point of the sample is measured by JIS. This is a graph in which this is plotted, the relational expression y = −32.129x + 48.048 is obtained therefrom, and this is drawn. The polluted diesel oil mixed with diesel oil in the range of 0 to 0.1% is applied to the gasoline contamination detector shown in FIG. 1 used in the example, the scale value is examined, and the flash point of the sample is measured by JIS. This is a graph in which this is plotted, the relational expression y = −73.751x + 74.308 is obtained therefrom, and this is drawn. It is a graph which shows the measurement result of the contamination detector of the polluted kerosene created based on Table 1. FIG. It is a graph which shows the measurement result of the contamination detector of the polluted light oil created based on Table 2. FIG. 1 is a simple determination table that can easily determine whether contaminated kerosene meets the JIS standard from the reaction tube scale value and measurement temperature obtained using the apparatus of FIG. 1, and can be used as a display board. 1 is a simple determination table that can easily determine whether or not the contaminated gas oil satisfies the JIS standard from the reaction tube scale value and measurement temperature obtained using the apparatus of FIG. 1, and can be used as a display board. Another specific example of the gasoline contamination detector of the present invention is shown. It is a perspective view which shows the state which accommodated the gasoline contamination detector of this invention in the trunk.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass bottle 2 Rubber stopper 3 Air introduction pipe 4 Sample 5 Gas phase (gas)
6 Vapor-liquid equilibrium gas supply pipe 7 Reaction tube 8 Suction means 9 Display panel 10 Reactant discoloration part

Claims (9)

Container that can store sample, lid or stopper of container, air introduction line for supplying air into sample in container, suction means for sucking gas-liquid equilibrium gas existing in container, suction means wherein the provided between the container, by including a reaction tube and the reaction tube with replaceable dummy tubes containing reactant which changes color by reaction with vaporized gasoline component of the gas-liquid equilibrium in the gas Gasoline contamination detector. Said suction means, gasoline contamination detector of claim 1, wherein as it can quantitatively aspirating gas in the system. The gasoline according to claim 1 or 2, wherein the reaction tube has a vaporized gasoline component concentration in the gas-liquid equilibrium gas of 10 ppm or more, and contains a reactant capable of changing a color change or coloring region according to the concentration. Contamination detector. Container that can store sample, lid or stopper of container, air introduction line for supplying air into sample in container, suction means for sucking gas-liquid equilibrium gas existing in container, suction means and provided between the container, reaction tubes containing reaction agent which changes color by reaction with vaporized gasoline component of the gas-liquid equilibrium in the gas, the and the reaction tube with replaceable dummy pipe, when the sample is kerosene A gasoline contamination detector characterized by comprising a judgment table for judging whether or not JIS K 2203 is satisfied or, if the sample is light oil, whether or not JIS K 2204 is satisfied . The gasoline contamination detector according to claim 4, wherein the reaction tube is provided with the same scale as the vertical axis of the judgment table .   Using the gasoline contamination detector according to any one of claims 1 to 3, a dummy tube is first attached, while the sample is placed in a container in which it can be stored, and then the gas phase portion is in gas-liquid equilibrium by suction means. After the gas in the gas phase in the container is sucked until the temperature reaches, the dummy tube is replaced with a “reaction tube containing a reagent that reacts and changes color” so that air does not enter the container. The gas in the gas phase in the container that has reached a certain amount of vapor-liquid equilibrium is sucked in by the suction means, and the part of the scale on the reaction tube that reads the discoloration of the reactant is read from this value. A method of estimating the flash point of a sample by detecting Using the gasoline contamination detector according to any one of claims 1 to 3, a dummy tube is first attached, while the sample is placed in a container in which it can be stored, and then the gas phase portion is in gas-liquid equilibrium by suction means. After the gas in the gas phase in the container is sucked until the temperature reaches, the dummy tube is replaced with a “reaction tube containing a reagent that reacts and changes color” so that air does not enter the container. The gas in the gas phase portion in the container that has reached a certain amount of vapor-liquid equilibrium is sucked by the suction means, and the portion of the scale of the reaction tube that has changed color is read, and the temperature of the sample in the container is the reference temperature 25. ° C. accept the scale of the reaction tube when the, when the temperature of the sample in the vessel temperature other than the reference temperature 25 ° C., to convert the value to scale value of the reaction tube of the reference temperature 25 ° C., to obtain Based on the scale value, How to estimate the flash point of the sample by detecting the degree of Ntami. Using the gasoline contamination detector according to any one of claims 1 to 3, a dummy tube is first attached, while the sample is placed in a container in which it can be stored, and then the gas phase portion is in gas-liquid equilibrium by suction means. After the gas in the gas phase in the container is sucked until the temperature reaches, the dummy tube is replaced with a “reaction tube containing a reagent that reacts and changes color” so that air does not enter the container. The gas in the gas phase in the container that has reached a certain amount of vapor-liquid equilibrium is sucked by the suction means, and to what part of the scale of the reaction tube the reagent has changed color, this value and the container at the time of measurement are read. and a temperature of the sample of the inner, in the case of kerosene using the determination table for kerosene, in the case of light oil by using a determination table for light oil, kerosene or gas oil as the object of measurement, respectively JIS K 2203 or JIS K 2204 pull How to judgment whether satisfying the conditions of the fire point. Using a gasoline contamination detector according to claim 4 or 5, a dummy tube is first attached, while the sample is placed in a container capable of storing it, and then the gas phase portion reaches vapor-liquid equilibrium by suction means. After sucking the gas in the gas phase part in the container until the air does not enter the container, the dummy tube is replaced with a “reaction tube containing a reagent that reacts and changes color”, and then a predetermined amount of The gas in the gas phase in the container that has reached vapor-liquid equilibrium is sucked by the suction means, and in the case of kerosene, the position corresponding to the temperature of the sample in the container in the kerosene judgment table, in the case of light oil, the judgment table for light oil Place the reaction tube at a position corresponding to the temperature of the sample in the container in parallel with the scale axis of the reaction tube, and if the boundary position between the discolored portion of the reaction tube and the non-discolored portion in the reaction tube is kerosene, "question in the judgment table Or in the region of no ", or in the region of the" necessary measures "or in the region of, or" read whether the region of the non-standard ", also in the case of light oil Nashi" problem in light oil determination table " The kerosene or light oil that is the subject of measurement by reading whether it is in the “necessary measurement” area or “non-standard” area is the flash point condition of JIS K 2203 or JIS K 2204 , respectively. method that determines whether meet.