JP2008281412A - Vaporizer used for measuring content of petroleum hydrocarbon component contained in soil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable a petroleum hydrocarbon component in a sample which is charged in a sample chamber, to be vaporized completely for a short time, and measure the content of the petroleum hydrocarbon component contained in a soil for a short time, by using a method in which the soil containing the petroleum hydrocarbon component is charged in the sample chamber of a vaporizer, and the heating process is applied in order to vaporize the component contained in the soil, and the vaporized component is fed to and burned in a reaction chamber, and the amount of generated carbon dioxide is measured in order to measure the content of the component contained in the soil. <P>SOLUTION: In the vaporizer, a mount section 4 of a sample holder having a mixed gas introducing part 5 at one end and an aperture part 6 at the other end is disposed inside a heating furnace 2, and an airtight ring 7 is attached around the sample holder 3, and the sample chamber 8 is formed therein so as to correspond to the mixed gas introducing part 5, and an exhaust channel 9 for a mixed gas containing the vaporized component is formed on the outlet side of the sample chamber 8, such that the exhaust channel 9 communicates with a reaction tube 17, and a gas diffusion layer 11 filled up with quartz wool etc. is disposed at the exhaust channel 9. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, soil containing petroleum hydrocarbon components is loaded into a sample chamber of a vaporizer 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. The present invention relates to a vaporizer used for a method of 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 chamber and burning it.

  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 chart (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)

  Moreover, the instrument which extracts the hydrocarbon of the soil extract | collected as a simple hydrocarbon analyzer in soil with an extraction solvent, and measures hydrocarbon content from the turbidity of an extract is marketed.

  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 the extract, light hydrocarbon fractions in the soil are evaporated by heating, trapped (purge and trap, PT), analyzed by GC, and from the area ratio of the chart A method for measuring the oil content (PT-GC method) is known (Technology Development Report on Purification of Petroleum-Contaminated Soil Issued by the Oil Industry Revitalization 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, Adopts a method of applying the carbon disulfide extraction-GC method (PEC method) using the above-described extract (Non-patent Document 1), and therefore a wide range of petroleum hydrocarbon components from light to medium heavy fractions. In the conventional methods, extraction operations using an organic solvent that causes air pollution or soil contamination have been used for soils containing any of the above.

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 loaded into 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 sent to a reaction chamber for combustion, 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 was proposed (Japanese Patent Application 2005-370876).
JP2003-294617, JP2003-302316, Technical Development Report on Purification of Oil-Contaminated Soil Issued by the Oil Industry Revitalization Center in March 2003

  However, in this method, when vaporizing petroleum hydrocarbon components contained in soil by heat, in order to measure all components of lower and higher hydrocarbons, a method of heating and heating a soil sample is However, it takes time for heating, and it is necessary to cool to room temperature each time a sample is introduced, and therefore, there is a disadvantage that analysis takes time.

  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 a petroleum system in soil proposed in Japanese Patent Application 2005-370876. It cannot be used as a vaporizer used in a method for measuring the hydrocarbon component content.

  Therefore, the present invention is a method for measuring the content of petroleum hydrocarbon components contained in the above-mentioned soil, and instantly completes the analysis in a short time by vaporizing the petroleum hydrocarbon components contained in the soil. The object is to develop a vaporizer that can do this.

  In view of the above circumstances, the present invention loads a soil containing a petroleum hydrocarbon component into a sample chamber of a vaporizer and heat-treats it to vaporize the component contained in the soil, and oxygen and nitrogen 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 gas mixture into the reaction tube and burning it The vaporizer comprises a heating furnace, a sample holder, and a sample holder mounting portion mounted in the heating furnace, and a mixed gas is introduced into one end of the sample holder mounting portion. An opening is provided at the first and second ends, and a communication path to the reaction tube is provided. On the other hand, inside the sample holder is a sample chamber corresponding to the introduction portion of the mixed gas, and vaporization is performed on the outlet side of the sample chamber. Forming a discharge path of the mixed gas containing minute, the exhaust Detchi proposes a vaporizer which is adapted to be connected to the communication path into the reaction tube.

  That is, in the present invention, the heating furnace is preheated to heat the sample holder mounting portion, and by mounting a sample holder loaded with a soil sample in the sample chamber, it takes time to heat the heating furnace, Petroleum hydrocarbon components in the soil sample can be vaporized, and it is not necessary to cool to room temperature each time the soil sample is introduced, and therefore analysis can be performed in a short time.

  In the present invention, by mounting an airtight ring such as an O-ring on the outer periphery of the sample holder, the airtightness between the sample holder and the wall surface of the mounting portion of the sample holder can be maintained when the sample holder is mounted in the heating furnace.

  In order to securely seal the sample holder and the wall surface of the sample holder mounting part, it is necessary to mount one or more airtight rings such as O-rings around the sample holder with a communication path between them. When the vaporization component in the soil sample is low or the heating furnace is set to a high temperature and the vaporization component in the soil sample is easily vaporized, the airtight ring is at the end of the discharge path from the communication path. It may be provided on the outer periphery of the side sample holder.

  Furthermore, in the present invention, by providing a gas diffusion layer filled with quartz wool or the like in the discharge path, the mixed gas containing the vaporized component discharged from the sample chamber can be introduced into the reaction tube while diffusing. .

The end of the discharge path is sealed with a plug member at the opening formed to fill the discharge path with quartz wool or the like. In this case, an airtight such as an O-ring is provided around the outer periphery of the plug material. If the ring is attached, the airtightness between the stopper member and the sample holder wall surface can be maintained when the stopper member is attached to the opening.

  In short, according to the present invention, the soil containing petroleum hydrocarbon components is loaded into the sample chamber of the vaporizer and heat-treated to vaporize the components contained in the soil, and oxygen and nitrogen are contained in the sample chamber. In a method of introducing a mixed gas and sending the vaporized component into a reaction chamber for combustion, measuring the amount of carbon dioxide generated thereby, and measuring the content of the component contained in soil, heating a heating furnace It is possible to completely evaporate the petroleum hydrocarbon components in the soil sample without spending time, and it is not necessary to cool to room temperature each time a soil sample is introduced. Can do.

  It consists of a heating furnace, a sample holder, and a sample holder mounting part provided in the heating furnace. The sample holder mounting part is provided with a mixed gas introduction part at the upper end and an opening part at the lower end, while the sample holder is Two or more hermetic rings are mounted on the upper and lower sides of the outer periphery, and inside the sample chamber corresponding to the mixed gas introduction part, and a discharge path for the mixed gas containing vaporized components is formed on the outlet side of the sample chamber. The discharge passage is communicated with the reaction tube, and is filled with quartz wool or the like from its lower end opening to provide a gas diffusion layer in the passage, and the lower end opening of the discharge passage is fitted with an airtight ring on the outer periphery. A vaporizer used to measure the content of petroleum hydrocarbon components in soil that is blocked by a member.

  Hereinafter, the present invention will be described in detail with reference to the illustrated embodiments. Reference numeral 1 denotes a vaporizer according to the present invention. The vaporizer 1 includes a heating furnace 2, a sample holder 3, and a sample holder 3 inside the heating furnace 2. A mounting portion 4 is provided, a mixed gas introducing portion 5 is provided at the upper end of the mounting portion 4, an opening 6 is provided at the lower end, and the sample holder 3 is inserted from the lower end opening 6 to attach the mounting portion. 4 is mounted inside.

  Grooves 20, 20 are formed on the outer periphery of the sample holder 3, and O-rings 7, 7 are attached to the grooves 20, 20. When the sample holder 3 is attached, the sample holder 3 and the attachment part 4 The airtightness between the walls is maintained.

  On the other hand, a sample chamber 8 is formed inside the sample holder 3, and a discharge path 9 for vaporized components and mixed gas is formed on the outlet side of the sample chamber 8. The mixed gas introduced from the mixed gas introducing part 5 at the upper end of the sample holder mounting part 4 contacts the soil sample filled in the sample chamber 8. Then, the hydrocarbon component in the soil sample is vaporized, and the mixed gas containing the vaporized component passes through the discharge passage 9 and the communication passage 10 and is sent to the reaction tube.

  In this embodiment, O-rings 7 and 7 are provided on the outer periphery of the sample holder 3 above the communication path 10 and below the communication path 10, respectively. When the heating furnace 2 is set to a high temperature and the vaporized component in the soil sample is easily vaporized, the vaporized component in the soil can be sufficiently vaporized simply by providing the O-ring 7 below the communication path 10. And airtightness can be maintained.

  A gas diffusion layer 11 is provided by filling the discharge passage 9 with quartz wool or the like, and a mixed gas containing a vaporized component discharged from the sample chamber 8 is diffused and introduced into the reaction tube.

  In this embodiment, an opening 12 is provided at the end of the discharge passage 9 for inserting quartz wool or the like. However, in order to maintain airtightness in the apparatus, the opening 12 is a plug member. 13 and an O-ring 14 is mounted on the outer periphery of the plug member 13 so that the plug member 13 and the outer wall surface of the sample holder 3 are kept airtight when the plug member 13 is mounted in the opening 12. It is.

  As described above, the vaporizer 1 connects the introduction part 5 of the mixed gas to the gas line 15, and further connects the communication path 10 to the reaction tube 17 filled with the combustion catalyst layer 16 to thereby make petroleum-based carbonization in the soil. It can be incorporated into a hydrogen content measurement apparatus.

  When measuring the content of petroleum-based hydrocarbon components in the soil using this measuring device, the sample holder mounting part 4 and the sample holder 3 provided inside the heating furnace 2 are separated and the heating furnace 2 is kept at a predetermined temperature. The sample chamber 8 of the sample holder 3 is heated to about 200 ° C. to 250 ° C., and a predetermined amount of soil sample 19 is loaded through the filter 18.

Next, when the sample holder 3 is mounted in the sample holder mounting portion 4 provided inside the heating furnace 2, the petroleum hydrocarbon component contained in the soil sample loaded in the sample chamber 8 is immediately vaporized. .

  At the same time, when the mixed gas is introduced from the gas line 15 into the sample holder mounting portion 4 provided in the heating furnace 2, the vaporized component is discharged from the sample chamber 8 along with the mixed gas.

  The mixed gas containing the vaporized component discharged from the sample chamber 8 passes through the discharge passage 9 and the communication passage 10 filled with the gas diffusion layer 11 and fills the combustion catalyst layer 16 made of, for example, Pt 0.3 wt% -alumina supported catalyst. It is sent to the reaction tube 17 and burned, and the amount of carbon dioxide generated thereby is measured, and the content of the component contained in the soil is measured from the amount of carbon dioxide.

Next, a vaporization experiment example using the vaporizer according to the present invention will be described.
Vaporization experiment example 1
A simulated contaminated soil was prepared by adding kerosene to a soil of 10000 mg / kg-soil. 1 g of the soil is loaded into the sample chamber 8 of the sample holder 3, while the heating furnace 2 is heated to 150 ° C., and then the sample holder 3 is mounted on the sample holder mounting portion 4 provided inside the heating furnace 2. Further, after the heating furnace 2 was heated at 150 ° C. for 1 to 5 minutes, the residual amount of each oil was measured, and the vaporization efficiency of the oil was examined.

  The residual amount of oil was measured using a gas chromatograph method. As a result, as shown in FIG. 5, by using the vaporizer according to the present invention, about 95% of the oil was vaporized in 1 minute, and in 3 minutes. It became clear that it completely vaporized.

Vaporization experiment example 2
Water was added to the soil at a rate of 5 mass% to prepare water-containing soil. Kerosene was added to make 10000 mg / kg-soil there, and water-containing simulated contaminated soil was prepared. 1 g of the soil is loaded into the sample chamber 8 of the sample holder 3, while the heating furnace 3 is heated to 150 ° C. and then the sample holder 3 is mounted on the sample holder mounting portion 4 provided inside the heating furnace 2, Further, after the heating furnace 2 was heated at 150 ° C. for 1 to 7 minutes, the residual amount of each oil was measured to examine the vaporization efficiency of the oil.

The residual amount of oil is measured using a gas chromatograph method. As a result, as shown in FIG. 6, about 97% of the oil is vaporized in 3 minutes by using the vaporizer according to the present invention. It became clear that it completely vaporized.

As a result, in the vaporization experiment example 1 using the soil containing no water, about 95% of the oil was vaporized in 1 minute and completely vaporized in 3 minutes. On the other hand, in the vaporization experiment example 2 using water-containing soil, about 97% of the oil was vaporized in 3 minutes, and it took 5 minutes to completely vaporize, but by heating any soil for 3 minutes, Most of the oil contained in the soil is vaporized. Therefore, the influence of moisture was negligible, and by using this apparatus, any soil was able to efficiently vaporize oil in the soil.

  In short, according to the present invention, in the method for measuring the content of the component contained in the soil, the petroleum hydrocarbon component in the soil sample is completely vaporized without taking time to heat the heating furnace. Each time a soil sample is introduced, it is not necessary to cool to room temperature. Therefore, the method for measuring the content of the component contained in the soil previously proposed by the present inventor is analyzed without taking time. It can be performed.

Explanatory drawing of the vaporization apparatus which concerns on this invention The figure which shows the state which decomposed | disassembled the vaporizer same as the above Enlarged view of the contact area between the sample holder and the sample holder mounting part in the same vaporizer Explanatory drawing of the content measuring device for petroleum-based hydrocarbon components in soil composed of the same vaporizer The figure which shows the relationship between the heating time in the vaporization experiment example 1, and the residual amount of TPH (petroleum hydrocarbon component) in a soil sample The figure which shows the relationship between the heating time in the vaporization experiment example 2, and TPH (petroleum type | system | group hydrocarbon component) residual amount in a soil sample.

Explanation of symbols

Reference numeral 1 denotes a vaporizer 2, a heating furnace 3, a sample holder 4, a sample holder mounting part 5, a mixed gas introducing part 6, a lower end opening 7 of the sample holder mounting part, 14 an O-ring 8, a sample chamber 9 a vaporizing component The mixed gas discharge passage 10 is connected to the reaction tube 11, the gas diffusion layer 12, the lower end opening 13 of the discharge passage, the plug member 15, the gas line 16, the combustion catalyst layer 17, the reaction tube 18, and the filter 19 is a soil sample. 20 is an O-ring mounting groove

Claims (6)

The soil containing the petroleum hydrocarbon component was loaded into the sample chamber of the vaporizer and heat-treated to vaporize the component contained in the soil, and the mixed gas of oxygen and nitrogen was vaporized by introducing the mixed gas into the sample chamber. A vaporizer used in a method of sending the component into a reaction tube to burn, 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 a mixed gas introduction part at one end and an opening part at the other end. Further, a communication passage to the reaction tube is provided, while a sample chamber corresponding to the introduction portion of the mixed gas is provided inside the sample holder, and a discharge passage for the mixed gas containing vaporized components on the outlet side of the sample chamber Formed, vaporizer, characterized in that the exhaust Detchi was so as to be connected to the communication path into the reaction tube. The vaporizer according to claim 1, wherein an airtight ring for maintaining airtightness with the sample holder mounting portion is mounted on an outer periphery of the sample holder. The vaporizer according to claim 2, wherein at least one airtight ring is attached to the outer periphery of the sample holder with a communication path interposed therebetween. 4. The vaporizer according to claim 2, wherein a mounting groove for an airtight ring is formed on the outer periphery of the sample holder. The vaporizer according to claim 1, wherein a gas diffusion layer formed by filling quartz wool or the like is provided in a discharge path of a mixed gas containing a vaporized component. An opening is formed at the end of the discharge path of the mixed gas containing the vaporized component, and a plug member for sealing the opening is provided, and an airtight ring for maintaining the airtightness with the sample holder on the outer periphery of the plug member The vaporizer of Claim 1 which mounted | wore.