JP5227858B2 - Vaporizer for measuring the content of hydrocarbon components in soil - Google Patents

Description

  The invention of the present application fills the sample chamber of the vaporizer with the soil containing the hydrocarbon component and heat-treats it to vaporize the component contained in the soil, and introduces a gas mixture of oxygen and nitrogen into the sample chamber and vaporizes the sample chamber. The present invention relates to a vaporizer used in a method for measuring the content of the component contained in soil by measuring the amount of carbon dioxide generated by sending the burned component into a reaction tube and burning it.

Hydrocarbon is an organic substance containing carbon and hydrogen, and examples of soil contamination include chemical products such as liquid fuel, solid fuel, biomass fuel, lubricating oil, and solvent.
Among these, one of the pollutants that are particularly common in soil contamination is petroleum hydrocarbons. Hereinafter, explanation will be given by taking petroleum hydrocarbon as an example.

  Petroleum hydrocarbons are derived from petroleum products handled at petroleum-related facilities and constitute gasoline, kerosene, light oil, heavy oil A, heavy fuel oil, lubricating oils (mineral oil, synthetic oil), crude oil, etc. Hydrocarbon compounds. Currently, the Soil Contamination Countermeasures Law has been enacted, and it is mandatory to report the results of soil contamination surveys when changing the use of land, and as part of this, the content of petroleum hydrocarbon components in the soil is often examined. .

As a conventional method for analyzing petroleum hydrocarbons, a method of extracting and separating petroleum hydrocarbon components in soil with n-hexane, evaporating n-hexane by heating, and measuring the weight of the residue (n -Hexane extraction-gravimetric method), extraction and separation of petroleum hydrocarbon components in the soil with carbon tetrachloride, and infrared absorption spectroscopic analysis (IR) of the carbon tetrachloride extract to measure the component content (Carbon tetrachloride extraction-IR method), petroleum hydrocarbon components in the soil are extracted and separated with carbon disulfide, and the carbon disulfide extract is analyzed by gas chromatography (GC, detection device FID). A method of measuring the component content from the area ratio of the chromatogram (carbon disulfide extraction-GC method) is known. (Technology development report on purification of oil-contaminated soil, published in March 2003 by the Petroleum Industry Activation Center). Also known is a method (tetrachloroethylene extraction-IR method) in which petroleum hydrocarbon components in the soil are extracted with tetrachloroethylene and the extract is subjected to IR analysis to measure the component content. (JP 2003-294617)

  In addition, as a simple analyzer for hydrocarbons in soil, instruments for extracting hydrocarbons in collected soil with an extraction solvent and measuring the hydrocarbon content from the turbidity of the extract are commercially available.

  In addition, as a method of measuring the oil content in water, after extracting the oil content in water with an extraction solvent, volatilizing the extraction solvent from the oil extract and measuring the oil content from carbon dioxide generated by burning the residue Is disclosed (Japanese Patent Laid-Open No. 2003-302316).

  However, these methods all use extracts that cause air pollution or soil contamination. Therefore, if these extracts are discharged as they are, environmental pollution will occur and these extracts will be rendered harmless. It takes a lot of money and effort.

  On the other hand, as a method that does not use an extract, light hydrocarbon fractions in the soil are evaporated by heating, trapped (purge and trap, PT), analyzed by gas chromatography, and the area of the chart The method of measuring the oil content from the ratio (PT-GC method) is known (Technology Development Report on Purification of Petroleum-Contaminated Soil Issued by the Oil Industry Activation Center in March 2003).

  However, this method is applied when the petroleum hydrocarbon component contained in the soil is a light fraction. When the medium heavy fraction is included in addition to the light fraction, the above-described extract is used. The carbon disulfide extraction-GC method (PEC method) is employed (Non-Patent Document 1), and therefore, for soil containing a wide range of petroleum hydrocarbon components from light to medium heavy fractions. In any of the conventional methods, extraction with an organic solvent that causes air pollution or soil pollution has been used.

  Therefore, the present inventor does not require extraction operation with an organic solvent for soil containing a wide range of petroleum hydrocarbon components from light fractions to medium heavy fractions, and simply measures the content of petroleum hydrocarbon components. As a method to do this, the soil containing petroleum hydrocarbon components is filled in the sample chamber of the heating section and heat-treated to vaporize the components contained in the soil, and a mixed gas of oxygen and nitrogen is introduced into the sample chamber Petroleum carbonization in soil, characterized in that the vaporized component is fed into a reaction tube and burned, the amount of carbon dioxide generated thereby is measured, and the content of the component contained in the soil is measured A method for measuring the hydrogen content has been proposed (Japanese Patent Laid-Open No. 2007-171049). In this method, in order to shorten the analysis time, the petroleum hydrocarbon components contained in the soil are instantly vaporized and shortened. Minute in time Development of gasifier can be completed is essential.

  Japanese Patent Application Laid-Open No. 5-126699 discloses a method of heating a solid sample and collecting and concentrating a volatile component in an adsorbent and introducing the sample into a measuring device by thermal desorption. Discloses a method for automatically replacing the liner of the gas chromatography inlet, both of which relate to gas chromatography, and previously proposed petroleum oil in soil proposed in Japanese Patent Application Laid-Open No. 2007-171049. It cannot be used in a method for measuring the content of hydrocarbon-based hydrocarbon components.

Therefore, the inventor of the present application, as shown in FIG. 10 as a vaporizer for use in the above method, includes a heating furnace 2, a sample holder 3, and a sample holder mounting portion 4 mounted in the heating furnace 2. The sample holder mounting part 4 is provided with a mixed gas introduction path 9 at the upper end and an opening 5 at the lower end, and further provided with a communication path 10 to the reaction tube. Correspondingly, a vaporizer was proposed in which a mixed gas discharge passage 10a containing vaporized components was formed on the lower outlet side of the sample chamber 6 (Japanese Patent Laid-Open No. 2008-281412).

JP2003-294617 JP2003-302316 JP2007-171049 Japanese Patent Laid-Open No. 5-126699 Special table 2003-510558 JP2008-281412

Technical Development Report on Purification of Oil-Contaminated Soil Issued by the Oil Industry Revitalization Center in March 2003

    In the vaporizer shown in FIG. 10, the mixed gas introduced from the upper end of the sample holder mounting portion 4 and the soil sample filled in the sample chamber 6 are heated by the heating furnace 2, whereby the petroleum hydrocarbons in the soil sample are vaporized. The amount of carbon dioxide that is sent to the reaction tube 10 along with the mixed gas, sent to the reaction tube, and combusted and generated is measured, and the content of the component contained in the soil is measured and heated by the gas heating line. Thus, the mixed gas and the soil sample filled in the sample chamber 6 can be brought into direct contact with each other, and the oil content in the soil sample can be effectively vaporized.

However, in order to reduce the size of the apparatus and increase the thermal efficiency, it is indispensable for the vaporizing apparatus to be used in the above method. However, in the vaporizing apparatus of FIG. Since it is mounted from the formed opening 5, a large space is required below the sample holder mounting portion 4, so that workability is poor, the apparatus is enlarged, and the constituent material is thick, As a result, the thermal efficiency of each component is poor, and there is a drawback that it takes time to vaporize hydrocarbons in the soil sample.

  Therefore, the present invention develops a vaporization apparatus that can reduce the size of the apparatus and reduce the thickness of the material used in the method for measuring the content of the hydrocarbon component contained in the soil, and can realize a simple measurement work. It is intended to do.

In view of the above situation, as a first invention of the present application, a soil sample containing a hydrocarbon component is filled in a sample chamber of a vaporizer and heat-treated to vaporize the component contained in the soil, and oxygen and nitrogen are contained in the sample chamber. A method of measuring the content of the component contained in the soil from the amount of carbon dioxide, by measuring the amount of carbon dioxide generated by sending the component vaporized by introducing the gas mixture into the reaction tube and burning it A vaporizer used for the heating, the vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting portion mounted in the heating furnace,
The sample holder mounting portion has an opening for mounting the sample holder at the upper end, while a sample chamber is provided at the bottom of the sample holder, and a soil sample filling port is provided at the upper end of the sample holder, The filling port is provided with an airtight stopper, and further on the side of the sample holder and the sample holder mounting part, above the sample chamber, a mixed gas introduction path and a mixed gas discharge path containing vaporized components communicating with the reaction tube, respectively. The vaporizer which formed this is proposed.

As a second invention of the present application, a soil sample containing a hydrocarbon component is filled in a sample chamber of a vaporizer and heated to vaporize the component contained in the soil, and a mixed gas of oxygen and nitrogen is introduced into the sample chamber. The vaporized apparatus used in the method of sending the vaporized component to the reaction tube and burning it, measuring the amount of carbon dioxide generated thereby, and measuring the content of the component contained in the soil from the amount of carbon dioxide The vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting portion mounted in the heating furnace.
The sample holder mounting part is provided with an opening for mounting the sample holder at the upper end, and an inlet for introducing a mixed gas of oxygen and nitrogen at the lower end, and a discharge path for discharging the vaporized component at the side. ,
The sample holder is provided with a soil sample filling port at its upper end, a sample chamber is provided in its interior, and a mixing gas communicating with a mixed gas introduction path provided in the sample holder mounting portion is provided at the bottom of the sample chamber. A gas introduction path is provided, and a side of the sample holder at the top of the sample chamber is provided with a discharge port communicating with a vaporization component discharge path provided in the sample holder mounting portion. The vaporization apparatus provided with is proposed.

In other words, in the first and second inventions of the present application, an opening is provided at the upper end of the sample holder mounting part, and the sample holder is mounted from this, as in the previous patent application (Japanese Patent Laid-Open No. 2008-281412). Without providing a space for mounting the sample holder, the apparatus can be reduced in size and the material used can be reduced in thickness.

In the first and second inventions of the present application, since the sample holder is mounted from the upper end of the sample holder mounting portion, the measurement work can be easily performed.

Among these, in the first invention of the present application, hydrocarbons in the soil sample are vaporized without directly contacting the mixed gas heated in the gas heating line with the soil sample. There are advantages such as complete vaporization in time.

In the first invention of the present application, the height of the mixed gas inlet and the mixed gas outlet including the vaporized component at the side of the sample holder is changed, or the diameter of the discharge path is made smaller than the diameter of the introduction path. Therefore, if the mixed gas moderately generates turbulence in the sample holder, the oil content in the soil sample can be efficiently vaporized.

Since the first invention of the present application is a structure for introducing the mixed gas and discharging the mixed gas containing the vaporized component from the introduction path and the discharge path respectively formed on the side of the sample holder and the sample holder mounting portion, It is preferable that an airtight ring is provided between the airtight plugs, and the airtight plug is kept airtight between the sample holder and the airtight plug when the airtight plug is provided at the filling port of the soil sample.

Furthermore, it is preferable to provide an airtight ring between the sample holder and the sample holder mounting portion to maintain the airtightness between the sample holder and the wall surface of the mounting portion of the sample holder.

Note that if the airtight ring is formed with a fitting groove on the outer periphery of the sample holder and fitted in the fitting groove, the sample holder can be reduced in size and airtightness can be maintained.

On the other hand, in the first invention of the present application, hydrocarbons in the soil sample are vaporized without directly contacting the mixed gas heated in the gas heating line with the soil sample. However, for hydrocarbons such as heavy oil, the vaporization efficiency is reduced and only about 90% of the vapor is obtained.

  Accordingly, the second invention of the present application provides, as an improvement of the first invention, a vaporizer capable of realizing complete vaporization of a wide range of hydrocarbon components from light fractions to medium heavy fractions contained in soil samples in a short time. It is.

In other words, in the second invention of the present application, the soil sample filled in the sample chamber is directly contacted with the mixed gas fed from the mixed gas introduction path through the heating line, and is mixed with the light fraction contained in the soil sample. A wide range of hydrocarbon components up to the heavy fraction can be completely vaporized in a short time.

  In the second invention of the present application, the soil sample filled in the sample chamber employs a structure in which the mixed gas fed from the mixed gas introduction path through the heating line is in direct contact with the soil sample, so that it is provided at the bottom of the sample chamber. It is preferable that a soil sample is fixed by a blow-up flow of the mixed gas by providing a filter between the mixed gas introduction path and the sample chamber, and further providing a filter in the upper portion of the sample chamber.

In the second invention of the present application, an airtight ring is provided between the sample holder and the inner peripheral wall surface below the discharge port of the sample holder mounting part, and the inner peripheral wall surface below the discharge port of the sample holder and the sample holder mounting part. Maintains airtightness, so that the mixed gas sent from the inlet provided in the sample holder mounting part is introduced only into the sample chamber to ensure direct contact with the soil sample filled in the sample chamber. It is preferable to efficiently vaporize the hydrocarbon.

Furthermore, in the second invention of the present application, an airtight ring is provided between the sample filling port and the airtight stopper, and between the sample holder and the upper inner peripheral wall surface of the sample holder mounting portion, whereby the vaporized component discharged from the soil sample is It is preferable to discharge only through the discharge path.

Note that the airtight rings provided at the upper and lower parts of the sample holder and the sample holder mounting part form fitting grooves on the outer periphery of the upper and lower parts of the sample holder. And airtightness can be maintained.

The measurement of mainly petroleum-based hydrocarbon components contained in soil has been described so far, but the present invention is not limited to the measurement of petroleum-based hydrocarbons, but hydrocarbon components contained in the same kind of soil, such as biotechnology When pollutants can be estimated from land use history such as ethanol, biobutanol, esterified oil of vegetable oil, vegetable oil hydrotreated oil, biomass fuel such as BTL (Biomass To Liquids), mixture of petroleum hydrocarbon and biomass fuel Of course, the molecular formula of the pollutant or the molecular formula of the representative pollutant can be estimated, and it can be applied to the measurement.

For example, when petroleum hydrocarbons are completely burned, the following reaction formula (1) can be applied, and the amount of hydrocarbon components can be calculated from the amount of carbon dioxide generated. For example, when the contaminated oil type is medium oil such as light oil or heavy oil A, the amount of hydrocarbon components can be calculated by using Equation 1 with m = 1 and n = 1.8.

C _m H _n + (m + n / 4) O ₂ → mCO ₂ + n / 2H ₂ O (1)

For example, in the case of biomass fuel containing oxygen, the following reaction formula (2) can be used simultaneously. The amount of hydrocarbon components can be calculated by estimating main polluted oil species by history survey, specifying the values of m, n, and k, and using equation (2).

_{C m H n O k + (} m + n / 4 - k / 2) O 2 → nCO 2 + m / 2H 2 O ······ (2)

  In short, the present invention fills a soil sample containing a hydrocarbon component into the sample chamber of the vaporizer and heat-treats it to vaporize the component contained in the soil, and a mixed gas of oxygen and nitrogen into the sample chamber. Vaporization used in a method of measuring the amount of carbon dioxide generated by sending the vaporized component introduced into the reaction tube and burning it, and measuring the content of the component contained in the soil from the amount of carbon dioxide The apparatus comprises a heating furnace, a sample holder, and a sample holder mounting part mounted in the heating furnace, and the sample holder mounting part is provided with an opening for mounting the sample holder at the upper end. The equipment required for promoting the vaporization of hydrocarbons in the packed sample can be reduced in size and the materials used can be reduced, and at the same time the measurement work can be simplified. .

In the first invention of the present application, hydrocarbons in the soil sample are vaporized without directly contacting the mixed gas heated in the gas heating line with the soil sample. Full vaporization can be performed.

In the second invention of the present application, the soil sample filled in the sample chamber is not limited to hydrocarbons having a boiling point lower than that of medium oil by directly contacting the mixed gas fed from the mixed gas introduction path through the heating line, A wide range of hydrocarbon components from light fractions to medium heavy fractions contained in soil samples can be completely vaporized in a short time.

The figure which shows the decomposition | disassembly state of the vaporization apparatus which concerns on this invention 1st invention Explanatory drawing of the content measuring device of hydrocarbon components in the soil constructed by incorporating the above vaporizer Figure showing the relationship between TPH (mg / kg) in terms of diesel oil addition and TPH concentration (mg / kg) by the complete combustion method using the vaporizer according to the first invention of the present application Explanatory drawing of the vaporization apparatus which concerns on this invention 2nd invention. Explanatory drawing of the method apparatus which measures the carbon dioxide amount generated using the vaporization apparatus concerning this invention 2nd invention, and measures content of this component contained in soil from this carbon dioxide amount The figure which shows the other Example of the sample holder used for the vaporization apparatus concerning this invention 2nd invention. Results of the vaporization performance comparison experiment using the vaporizer according to the first invention of the present application (FIG. 1) and the vaporizer according to the second invention of the present application (FIG. 4) performed using simulated contaminated soil prepared by adding light oil to clean soil. Illustration The figure which shows the vaporization performance comparison experiment result by the vaporizer by this invention 1 invention (FIG. 1) and the vaporizer by this invention 2 invention (FIG. 4) performed using C heavy oil containing real soil Vaporization performance comparison experiment using the vaporizer according to the first invention of the present invention (FIG. 1) and the vaporizer according to the second invention of the present invention (FIG. 4), which was performed using simulated contaminated soil prepared by adding lubricating oil to clean soil Figure showing the results Explanatory drawing of the vaporizer according to JP2008-281412

It comprises a heating furnace, a sample holder, and a sample holder mounting part mounted in the heating furnace. The sample holder mounting part has an opening for mounting the sample holder at the upper end, and oxygen and nitrogen at the lower end. A mixed gas introduction path, a discharge path for discharging the vaporized component on the side, a soil sample filling port at the upper end of the sample holder, and a sample chamber inside the sample holder. Provided at the bottom of the sample chamber is a mixed gas introduction path that communicates with the mixed gas introduction path provided in the sample holder mounting section, and further on the side of the sample holder that contacts the top of the sample chamber. Vaporizing device provided with a discharge port communicating with the provided vaporization component discharge passage, and provided with an airtight plug at the sample filling port

  Hereinafter, the first invention of the present application will be described based on the illustrated embodiment. FIG. 1 is a vaporizer according to the present invention. The vaporizer 1 includes a heating furnace 2, a sample holder 3, and a sample holder inside the heating furnace 2. 3 is provided, and an opening 5 is provided at the upper end of the sample holder mounting part 4.

  On the other hand, the sample holder 3 is provided with a sample chamber 6 at the bottom, and a soil sample filling port 7 is provided at the upper end of the sample holder 3 so that the soil sample filling port 7 can be held airtight by an airtight plug 8. is there.

  Further, on the sides of the sample holder 3 and the sample holder mounting portion 4, a mixed gas introduction path 9 is provided above the sample chamber 6, and a mixed gas discharge path 10 containing a vaporized component communicating with the introduction port 9 a and the reaction tube, A discharge port 10a is formed.

  Note that the mixed gas inlet 9a in the side portion of the sample holder 3 and the mixed gas introduction path 9 in the sample holder mounting portion 4 communicating therewith and the mixed gas discharge port 10a containing the vaporized component and the sample holder mounting portion 4 communicating therewith. The height of the mixed gas discharge path 10 containing the vaporized component in the sample is changed, and the mixed gas inlet 9a in the side portion of the sample holder mounting portion 4 and the diameter of the mixed gas inlet path 9 in the sample holder mounting portion 4 communicating therewith are changed. By reducing the diameter of the mixed gas discharge port 10a containing the vaporized component and the diameter of the mixed gas discharge path 10 containing the vaporized component in the sample holder mounting portion 4 communicating therewith, the mixed gas causes moderate turbulence in the sample holder. It is.

  The sample holder 3 is mounted in the sample holder mounting portion 4 through the opening 5 of the sample holder mounting portion 4, and an airtight ring 11 is provided on the outer periphery of the sample holder 3, so that the sample holder 3 and the sample holder mounting portion are provided. The airtightness with the four wall surfaces is maintained.

  The soil sample is filled into the sample chamber 6 through the soil sample filling port 7, and after the filling, the hermetic plug 8 is screwed into the screw groove 12 formed on the outer periphery of the sample holder 3 to plug the soil sample filling port 7. An airtight ring 13 is provided on the outer periphery of the upper end so as to keep the airtightness between the sample holder 3 and the wall surface of the airtight stopper 8.

  As described above, the vaporizer 1 connects the mixed gas introduction path 9 to the gas line 14 and further connects the mixed gas discharge path 10 containing the vaporized component to the reaction tube 15 filled with the combustion catalyst. It can be incorporated into a content measuring device for hydrocarbon components therein. (Figure 2)

  When measuring the content of hydrocarbon components in the soil using this measuring apparatus, the sample holder mounting part 4 and the sample holder 3 provided inside the heating furnace 2 are separated, and the heating furnace 2 has a predetermined temperature of 150 ° C. to The sample chamber 6 of the sample holder 3 is filled with a predetermined amount of soil sample by heating to about 350 ° C., preferably about 250 ° C. to 350 ° C., more preferably about 280 ° C. to 320 ° C.

  Next, when the sample holder 3 is mounted in the sample holder mounting portion 4 provided inside the heating furnace 2, the hydrocarbon component contained in the soil sample mounted in the sample chamber 6 is immediately vaporized.

  At the same time, when the mixed gas is introduced from the gas line 14 into the sample holder mounting portion 4 provided in the heating furnace 2, the vaporized component is discharged from the sample chamber 6 along with the mixed gas.

  The mixed gas containing vaporized components discharged from the sample chamber 6 is sent through a discharge passage 10 to a reaction tube 15 filled with a combustion catalyst composed of, for example, Pt 0.3 wt% -alumina-supported catalyst, and burned. The measured carbon dioxide amount is measured, and the content of the component contained in the soil is measured from the carbon dioxide amount.

Next, a vaporization experiment example using the vaporizer according to the present invention will be described.
Vaporization experiment example 1
Simulated contaminated soil was prepared by adding light oil to clean soil. This soil was subjected to petroleum combustion measurement by a complete combustion type using the vaporizer according to the first invention of the present application, and the performance of the vaporizer of the present application was evaluated from the correlation of the petroleum hydrocarbon concentration with the simulated contaminated soil. The following reaction formula (1) was used for conversion from carbon dioxide, and in this case, m = 1 and n = 1.8. In this example, carbon dioxide was measured using a detector tube for carbon dioxide manufactured by Gastec.

C _m H _n + (m + n / 4) O ₂ → mCO ₂ + n / 2H ₂ O (1)

  As a result, the petroleum hydrocarbon concentration (TPH concentration) calculated from the added amount of light oil almost coincided with the petroleum hydrocarbon concentration by the complete combustion formula, and a high correlation was obtained (see FIG. 3).

  From this, it is considered that the hydrocarbon in the soil sample was completely vaporized by using the vaporizer according to the present application, and further completely burned. Therefore, it was proved that the complete vaporization of hydrocarbons in the soil is possible with the vaporizer according to the present application.

  Hereinafter, the second invention of the present application will be described in detail based on the embodiment of FIG. 4, wherein 1 is a vaporizer according to the present invention, and the vaporizer 1 is inside the heating furnace 2, the sample holder 3, and the heating furnace 2. A sample holder mounting portion 4 of the sample holder 3 is provided.

An opening 5 for mounting the sample holder 3 is provided at the upper end of the sample holder mounting portion 4, and an introduction path 9 for a mixed gas of oxygen and nitrogen is provided at the lower end. A discharge path 10 for discharging is provided.

  The sample holder 3 is provided with a soil sample filling port 7 at its upper end, a sample chamber 6 is provided therein, and a mixed gas introduction path provided in the sample holder mounting portion 4 is provided at the bottom of the sample chamber 6. 9 is provided with a mixed gas inlet 9a that communicates with the gas chamber 9, and a discharge port 10a that communicates with the vaporization component discharge passage 10 provided in the sample holder mounting portion 4 at the side of the sample holder 3 that is the upper portion of the sample chamber 6. Is provided.

On the other hand, an airtight stopper 8 is provided at the soil sample filling port 7, and the soil sample is further inserted into the sample chamber 6 through the filling port 7, but the mixed gas provided at the bottom of the sample chamber 6 is introduced. A filter 16a is provided between the mouth 9a and the sample chamber 6, and a filter 16b is provided in the upper portion of the sample chamber 6 so that the soil sample is fixed.

  The sample holder 3 is mounted in the sample holder mounting portion 4 through the opening 5, but an airtight ring 17 is provided on the outer periphery below the discharge port 10 a of the sample holder 3, so that the sample holder 3 and the sample holder mounting portion are provided. The airtightness with the inner peripheral wall surface below the discharge port 4 is maintained.

Thereby, since the mixed gas sent from the introduction path 9 is introduced into the sample chamber 6 only from the introduction port 9a, it is surely brought into direct contact with the soil sample filled in the sample chamber 6, so Hydrocarbons can be efficiently vaporized.

  On the other hand, an airtight ring 13 is provided on the outer periphery of the filling port of the sample holder 3 to maintain the airtightness of the filling port 7 when the airtight stopper 8 is plugged, and an airtight ring 11 is provided on the outer periphery of the upper portion of the sample holder 3. The airtightness between the sample holder 3 and the upper inner wall surface of the sample holder mounting portion 4 when the sample holder 3 is mounted on the mounting portion 4 is maintained. Therefore, the vaporized component discharged from the soil sample is discharged from the discharge path 10. 10a is sent to the reaction tube only.

As shown in FIG. 6, the sample holder 3 is formed by forming fitting grooves 18 and 19 on the upper outer periphery and the lower outer periphery of the sample holder 3, and fitting the airtight rings 11 and 17 in the grooves. 3 can be miniaturized to maintain hermeticity.

As described above, the vaporizer 1 connects the mixed gas introduction path 9 to the gas line 14 and further connects the mixed gas discharge path 10 containing the vaporized component to the reaction tube 15 filled with the combustion catalyst. It can be incorporated into a content measuring device for hydrocarbon components therein.

When measuring the content of hydrocarbon components in the soil using this measuring apparatus, the sample holder mounting part 4 and the sample holder 3 provided inside the heating furnace 2 are separated, and the heating furnace 2 has a predetermined temperature of 150 ° C. to Heat to about 350 ° C., preferably about 250 ° C. to 350 ° C., more preferably about 280 ° C. to 320 ° C., and the sample chamber 6 of the sample holder 3 is filled with a predetermined amount of soil sample.

  Next, when the sample holder 3 is mounted in the sample holder mounting portion 4 provided inside the heating furnace 2, and simultaneously with this, the mixed gas is introduced from the gas heating line 14 and the mixed gas introduction paths 9, 9a, the mixed gas Since it is in direct contact with the soil sample filled in the sample chamber 6, hydrocarbon components such as heavy oil contained in the soil sample are immediately vaporized.

The mixed gas containing the vaporized component discharged from the sample chamber 6 passes through the discharge passages 10 and 10a and is sent to the reaction tube 15 filled with a combustion catalyst composed of, for example, Pt 0.3 wt% -alumina-supported catalyst for combustion. The amount of carbon dioxide generated is measured, and the content of the component contained in the soil is measured from the amount of carbon dioxide.

Vaporizer performance comparison experiment example 1
Simulated contaminated soil was prepared by adding light oil to clean soil. About 1 g of the soil described above is based on an oil content measuring device using the vaporizer according to the first invention of the present application (FIG. 1) and a complete combustion type of oil in soil using the vaporizer according to the second invention of the present application (FIG. 4). Using oil content measuring equipment, measure the content of hydrocarbon components in soil (TPH measured concentration), and issue these values for the purification of oil-contaminated soil issued by the Japan Petroleum Industry Activation Center in March 2003. FIG. 7 shows the results of evaluating the performance of each vaporizer in comparison with the carbon disulfide extraction-GC method described in the technical development report.

The result of FIG. 7 shows that the TPH concentration was measured using a complete combustion type oil content measuring device using the vaporizer according to the first invention of the present application (FIG. 1) and the vaporizer according to the second invention of the present application (FIG. 4). Divided by the value obtained by the carbon disulfide extraction-GC method described above, and the oil content in the soil is completely burned, and the oil content is measured from the amount of generated carbon dioxide. In this method, (1) shows the one using the vaporizer according to the first invention of the present application (FIG. 1), (2) shows the one using the vaporizer according to the second invention of the present application (FIG. 4), and the value of the figure is The closer to 1.0, the higher the measurement accuracy.

As a result, in the light oil simulated contaminated soil, when the vaporizer according to the first invention of the present application (FIG. 1) is used, when the vaporizer according to the second invention of the present application (FIG. 4) is used, the above-described carbon disulfide extraction-GC Comparing the measurement of the method, both are about 1.0. This is because there is no difference in the performance of the vaporizer in the method of measuring the oil content from the amount of carbon dioxide generated by completely burning the oil content in the soil as described above until medium oil, and it is possible to measure almost all of them It turns out that it is.

Vaporizer performance comparison example 2
About 1 g of C heavy oil-containing real soil, the oil content measuring device using the vaporizer (Fig. 1) according to the first invention of the present application and the oil content in the soil using the vaporizer (Fig. 4) of the second invention of the present application. Using a complete combustion type oil content measuring device, measure the content of hydrocarbon components in soil (TPH measured concentration), and issue these values to the Oil Industry Activation Center in March 2003. Oil pollution FIG. 8 shows the results of evaluating the performance of each vaporizer in comparison with the carbon disulfide extraction-GC method described in the technical development report on soil purification.

The results of FIG. 8 are the same values as those of the vaporizer performance comparison experimental example 1, and the vaporization according to the first invention of the present application is performed in the described method for completely burning the oil in the soil and measuring the oil from the amount of generated carbon dioxide. The value obtained by measuring the TPH concentration using the oil content measuring device based on the complete combustion type of oil content in the soil using the device (FIG. 1) and the vaporization device according to the second invention of the present application (FIG. 4) (1) is a method in which the oil content in the soil is completely burned and the oil content is measured from the amount of generated carbon dioxide. The apparatus using the vaporizer according to the invention (FIG. 1), (2) shows the apparatus using the vaporizer according to the second invention of the present application (FIG. 4).

In addition, the carbon disulfide extraction-GC method described above measures up to the n-C44 component, and high boiling point hydrocarbons containing the n-C44 component or more are measured as a value smaller than the actual addition amount.

As is apparent from FIG. 8, when the vaporizer according to the first invention of the present application is used, it is about 0.80, but when the vaporizer according to the second invention of the present application is used, it is about 1.4.

Therefore, in the high boiling point hydrocarbon containing n-C44 component or more like C heavy oil, the vaporization apparatus according to the first invention of the present application does not completely vaporize, and the resulting TPH concentration is The value was lower than the carbon disulfide extraction-GC method described. On the contrary, when the vaporizer according to the second invention of the present application is used, it is possible to vaporize hydrocarbons having a high boiling point higher than the n-C44 component, and as a result, the carbon disulfide extraction-GC method described above is used. A value was also obtained for fractions of n-C44 equivalent fraction or more that could not be obtained, and a value higher than that of the carbon disulfide extraction-GC method described above was obtained.

Therefore, by using the second invention of the present application, it is proved that high boiling point hydrocarbons can also have high vaporization efficiency, and the method for measuring oil content from the amount of generated carbon dioxide by completely burning oil content in soil is described above. It was found that the high-boiling hydrocarbons that cannot be measured can be measured by the carbon sulfide extraction-GC method.

Vaporizer performance comparison example 3
About 1 g of soil prepared by adding lubricating oil to clean soil to prepare a simulated contaminated soil, a device for measuring oil content in a complete combustion type of oil in soil using the vaporizer (Fig. 1) according to the first invention of the present application, 2 Using a device for measuring oil content in the soil (TPH measured concentration) using a complete combustion type oil content measuring device using the vaporizer according to the invention (Fig. 4), and measuring these values , Issued by the Petroleum Industry Activation Center in March 2003. Figure 9 shows the results of evaluating the performance of each vaporizer compared to the carbon disulfide extraction-GC method described in the technical development report on purification of oil-contaminated soil. Shown in

The results of FIG. 9 are the same values as in the vaporizer performance comparison experimental example 1, and (1) is a method for measuring the oil content from the amount of generated carbon dioxide by completely burning the oil content in the soil as described above. The vaporizer according to the first invention (FIG. 1) is used, and (2) shows the vaporizer according to the second invention of the present application (FIG. 4). The closer the value of the figure is to 1.0, the higher the measurement accuracy.

As shown in FIG. 9, as a result, in the lubricating oil simulated contaminated soil, when using the vaporizer according to the first invention of the present application (FIG. 1), when using the vaporizer according to the second invention of the present application (FIG. 4), Compared to the carbon disulfide extraction-GC method measurement described above, both are about 1.0, so the oil content in the soil described above is completely burned up to medium oil, and the amount of carbon dioxide generated From the above, it can be seen that there is no difference in the performance of the vaporizer in the method of measuring the oil content, and all of them can be measured close to true values. In other words, it has been proved that high vaporization efficiency can be obtained for the lubricating oil by using any of the vaporizers according to the first and second inventions of the present application.

  In short, according to the present invention, a soil sample containing a hydrocarbon component is filled in the sample chamber of the vaporizer and heat-treated to vaporize the component contained in the soil, and the sample chamber is mixed with oxygen and nitrogen. Introduce gas and vaporize the component into the reaction tube to burn, measure the amount of carbon dioxide generated by this, and use it in the method of measuring the content of the component contained in the soil from the amount of carbon dioxide The vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting portion mounted in the heating furnace, and the sample holder is mounted on the upper end of the sample holder mounting portion. An opening for introducing a mixed gas of oxygen and nitrogen at the lower end, a discharge passage for discharging the vaporized component at the side, and an upper end of the sample holder. Provides a sample sample filling port, a sample chamber inside, a sample gas chamber at the bottom of the sample chamber, and a gas mixture introduction channel communicating with the gas mixture introduction channel provided at the sample holder mounting part. The side of the sample holder that hits the upper part of the chamber is provided with a discharge port communicating with the vaporization component discharge path provided in the sample holder mounting portion, and an airtight plug is provided at the soil sample filling port, thereby reducing the size of the apparatus. And thinning of the materials used and simple measurement work are possible, and complete vaporization of a wide range of hydrocarbon components from light fractions to medium heavy fractions contained in soil samples can be realized in a short time.

1 is a vaporizer 2 a heating furnace 3 a sample holder 4 a sample holder mounting portion 5 an opening 6 a sample chamber 7 a filling port 8 an airtight plug 9 a mixed gas introduction path 9 a is a mixed gas introduction port 10 A mixed gas discharge passage 10a containing a vaporized component is provided with gas mixture outlets 11, 13, 17 containing a vaporized component, an airtight ring 12, a screw groove 14, a gas line 15 and a reaction tube 16a, and 16b fitted with filters 18 and 19. Groove

Claims (15)

A soil sample containing a hydrocarbon component is filled in a sample chamber of a vaporizer and heat-treated to vaporize the component contained in the soil, and the mixed gas of oxygen and nitrogen is vaporized by introducing the mixed gas into the sample chamber. A vaporizer used in a method of sending a component into a reaction tube and burning it, measuring the amount of carbon dioxide generated thereby, and measuring the content of the component contained in soil from the amount of carbon dioxide, The vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting part mounted in the heating furnace,
The sample holder mounting portion has an opening for mounting the sample holder at the upper end, while a sample chamber is provided at the bottom of the sample holder, and a soil sample filling port is provided at the upper end of the sample holder, The filling port is provided with an airtight stopper, and further on the side of the sample holder and the sample holder mounting part, above the sample chamber, a mixed gas introduction path and a mixed gas discharge path containing vaporized components communicating with the reaction tube, respectively. A vaporizing device characterized by forming The vaporizer according to claim 1, wherein a turbulent flow of the mixed gas is generated in the sample holder by changing a height of the mixed gas introduction port and a mixed gas discharge port including a vaporized component at a side portion of the sample holder. 2. The vaporizer according to claim 1, wherein a turbulent flow of the mixed gas is caused in the sample holder by making the diameter of the discharge path smaller than the diameter of the introduction path. The vaporizer according to claim 1, wherein an airtight ring is provided between the sample holder and the airtight stopper. The vaporizer according to claim 1, wherein an airtight ring is provided between the sample holder and the sample holder mounting portion. 6. The vaporizer according to claim 5, wherein a fitting groove is formed on the outer periphery of the sample holder, and an airtight ring is fitted into the fitting groove. A soil sample containing a hydrocarbon component is filled in a sample chamber of a vaporizer and heat-treated to vaporize the component contained in the soil, and the mixed gas of oxygen and nitrogen is vaporized by introducing the mixed gas into the sample chamber. A vaporizer used in a method of sending a component into a reaction tube and burning it, measuring the amount of carbon dioxide generated thereby, and measuring the content of the component contained in soil from the amount of carbon dioxide, The vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting part mounted in the heating furnace,
The sample holder mounting part is provided with an opening for mounting the sample holder at the upper end, and an inlet for introducing a mixed gas of oxygen and nitrogen at the lower end, and a discharge path for discharging the vaporized component at the side. ,
The sample holder is provided with a soil sample filling port at its upper end, a sample chamber is provided in its interior, and a mixing gas communicating with a mixed gas introduction path provided in the sample holder mounting portion is provided at the bottom of the sample chamber. A gas introduction path is provided, and a discharge port communicating with a vaporization component discharge path provided in the sample holder mounting portion is provided on the side of the sample holder corresponding to the upper portion of the sample chamber.
A vaporizer characterized in that an airtight stopper is provided at the filling port of the sample. The vaporizer according to claim 7, wherein a filter for fixing the soil sample is provided between the mixed gas introduction path provided at the bottom of the sample chamber and the sample chamber. 8. A filter for fixing a soil sample is provided between the introduction path of the mixed gas provided at the bottom of the sample chamber and the sample chamber, and a filter for fixing the soil sample is provided above the sample chamber. The vaporizer described. Between the sample filling port and the airtight plug, between the sample holder and the upper part of the sample holder mounting part to the upper inner wall surface, below the sample holder and the lower part of the sample holder mounting part, from the mixed gas introduction path The vaporizer according to claim 7, wherein an airtight ring is provided between each of the upper inner peripheral wall surfaces. The vaporizer according to claim 10, wherein fitting grooves are formed in an upper outer periphery and a lower outer periphery of the sample holder, and an airtight ring is fitted in the fitting groove. The vaporizer according to claim 1 or 7, wherein the hydrocarbon component contained in the soil sample is petroleum hydrocarbon. The vaporizer according to claim 1 or 7, wherein the hydrocarbon component contained in the soil sample is biomass fuel. The vaporizer according to claim 1 or 7, wherein the hydrocarbon component contained in the soil sample is a mixture of petroleum hydrocarbon and biomass fuel. The vaporizer according to claim 13 or 14, wherein the biomass fuel is bioethanol, biobutanol, esterified oil of vegetable oil, vegetable oil hydrotreated oil, or BTL.

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