JP2001124748A - Method and apparatus for high-speed analysis of chlorobenzene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus, for an analysis, in which chlorobenzene as a substitution index of dioxins can be analyzed quickly regarding a waste-incinerator exhaust gas such as a refuse-incinerator exhaust gas or the like whose content of chlorobenzene is smaller that in conventional cases. SOLUTION: This high-speed analyzer for chlorobenzene by this invention is constituted in such a way that it comprises a permeator 1 in which a silicone resin hollow fiber membrane 10 is housed in an outer tube 11, that it comprises an adsorption pipe 2 into which an adsorbent is filled, that it comprises a power supply 3 which heats the adsorption pipe and that it comprises a gas chromatograph 4 which is provided with an electron capture detector. An exhauset gas 9 is passed through the hollow part of the hollow fiber membrane 10, chlorobenzene is permeated into the outer tube 11, the permeated chlorobenzene is adsorbed by the adsorption pipe 2, the adsorption pipe 2 is then heated, and the chlorobenzene is adsorbed so as to be analyzed by the gas chromatograph 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for high-speed analysis of chlorobenzene contained in gas discharged from combustion exhaust gas when general waste and industrial waste are incinerated in an incinerator. is there.

[0002]

2. Description of the Related Art In general, when incinerating various kinds of wastes, highly toxic dioxins may be generated in exhaust gas discharged from an incinerator. The concentration of dioxins in the exhaust gas is extremely small, such as dioxin and its homologues, dibenzofuran and its homologues, coplanar PCB, and the like, all of which are as low as about 1 ng / Nm ³ (equivalent value of toxicity) or less. Due to the large number, it is not possible with current technology to measure directly from the exhaust gas.

[0003] Therefore, Journal of the Air Pollution Society No. 28 No. 5 No. 2
As described on page 74 (1993), chlorobenzenes, which are precursors present at relatively high concentrations compared to dioxins, have a high degree of correlation with dioxins. There is a method of calculating and calculating the concentration of dioxins having a dirt. There is also a method for measuring chlorophenols as described in Ishikawajima Harima Technical Report Vol. 33, No. 5, 1993. Therefore, it is extremely important to accurately determine chlorobenzenes or chlorophenols in exhaust gas.

As an automatic analysis technique for chlorobenzenes and chlorophenols in exhaust gas, Japanese Patent Application Laid-Open No.
-153590 and JP-A-10-153590
Is described in Japanese Patent Application Publication No. The automatic analysis technology for analyzing chlorobenzenes and chlorophenols as an alternative index of dioxins described in these publications is a trap for removing water vapor contained in exhaust gas, a concentration filled with a resin adsorbent A line equipped with a tube, a heater capable of heating the condensing tube, a cold trap, and a gas chromatograph device, and a line for passing exhaust gas through the condensing tube, and a cold trap device for further condensing the adsorbed substance adsorbed on the condensing tube, to a cold trap And a line for sending the adsorbed matter concentrated in the apparatus to a gas chromatograph apparatus.

[0005] In the analysis by the automatic analysis technology of the above publication,
The exhaust gas is drawn by a pump downstream of the concentrator tube and passes through the concentrator tube after the trap removes water vapor and dust. At this time, chlorobenzenes and chlorophenols in the exhaust gas are adsorbed by the resin adsorbent filled in the concentration tube. Next, the temperature of the concentration tube was raised to 300 ° C., and at the same time, the line was switched so that the carrier gas of the gas chromatograph was passed through the concentration tube, and concentrated in a cold trap portion at −30 ° C. Heat to ° C. and send to gas chromatograph. Thus, the adsorbed chlorobenzenes and chlorophenols are desorbed and quantified by a gas chromatograph.

In recent years, the concentration of chlorobenzenes and chlorophenols in exhaust gas from incinerators has been decreasing, and especially the concentration of chlorobenzenes and chlorophenols other than monochlorobenzene is low. It has become. In such a case, in the measurement of chlorobenzenes, it is effective to selectively measure only monochlorobenzene having a relatively high concentration to maintain the measurement accuracy.

[0007] As a method for high-speed analysis of monochlorobenzene, there is a method described in JP-A-10-332666. The high-speed analysis method for monochlorobenzene as an alternative index of dioxins uses a trap for removing water vapor contained in exhaust gas, an adsorption tube filled with a resin adsorbent, and a concentration tube filled with a resin adsorbent. A line that sends the exhaust gas from the adsorption tube to the concentration tube with a heater that can be independently heated, a cold trap device for further concentrating the adsorbate in the concentration tube, a gas chromatograph device, and a gas chromatograph device for the adsorbate from the cold trap device And a line to be sent to the base station.

In the above-described method for analyzing monochlorobenzene at a high speed, the exhaust gas is drawn by a pump located downstream of the adsorption tube, and water vapor and dust are removed by a trap.
The solution is passed through an adsorption tube heated to ℃ 80 ° C., and then to a concentration tube maintained at 0 ° C. to 10 ° C. At this time, chlorobenzenes and chlorophenols other than monochlorobenzene in the exhaust gas are adsorbed by the resin adsorbent of the adsorption tube, and only monochlorobenzene is adsorbed by the resin adsorbent of the concentration tube. next,
The temperature of the concentrating tube was raised to 300 ° C., and at the same time, the line was switched so that the carrier gas of the gas chromatograph was passed through the concentrating tube. It is heated and sent to a gas chromatograph. As a result, the adsorbed monochlorobenzene is desorbed and quantified by the gas chromatograph in about 10 minutes.

[0009]

As described above, since the exhaust gas of recent waste incinerators generally has a low concentration of chlorobenzenes, a large amount of exhaust gas is sucked into the measuring device for a long time. It is necessary to concentrate by adsorbing on an adsorbent filled in a concentrating tube.

The exhaust gas from a refuse incinerator contains not only homologues and isomers of chlorobenzenes, but also various compounds produced in the combustion process. Since it is necessary to separate and quantify each compound from a mixture of these compounds, measurement (analysis) of chlorobenzenes is generally performed.
In many cases, a gas chromatograph is used.

In this gas chromatograph device,
Each compound in the exhaust gas is separated by interaction such as adsorption to a column of a gas chromatograph. However, it generally takes about 30 minutes to separate all the various compounds in the exhaust gas. Furthermore, in addition to the compound separation treatment by the gas chromatograph, before and after the treatment, adsorption and concentration of the compound in the exhaust gas, re-concentration, regeneration of the adsorbent filled in the concentration tube, cooling of the gas chromatograph (before analysis) (Returning to the initial state).

When these processing times are included, one measurement requires about one hour or more of analysis time. For this reason, it is difficult to control the combustion by quickly feeding back the measured values of chlorobenzenes. As described above, the conventional technique has a problem that it is difficult to estimate the concentration of dioxins from a low concentration of chlorobenzenes in a short time.

Also, in the prior art for selectively measuring only monochlorobenzene as an alternative index for dioxins, it is necessary to control the temperature of the adsorption tube, the concentration tube and the cold trap device independently. It is necessary to provide a power supply and a controller for control, and in addition, there is a problem that the operation of valves for collecting exhaust gas and exhausting the inside of the apparatus is complicated.

The present invention has been made to solve these problems, and is intended to be used as a substitute index for dioxins in waste incinerator exhaust gas such as waste incinerator exhaust gas containing less chlorobenzene than conventional ones. An object of the present invention is to provide a high-speed analysis method and an analysis device that enable rapid measurement of chlorobenzene.

[0015]

The high-speed analysis method for chlorobenzene according to the present invention is an analysis method for analyzing chlorobenzene in a gas, wherein the gas is passed through a hollow portion of a hollow fiber membrane, Chlorobenzene is selectively permeated to the outside of the hollow fiber membrane, the selectively permeated chlorobenzene is collected by an adsorbent, and then the chlorobenzene is desorbed from the adsorbent by heating and measured by a gas chromatograph. It is.

A first chlorobenzene high-speed analyzer according to the present invention is an analyzer for analyzing chlorobenzene in a gas, wherein the hollow fiber membrane is housed in an outer tube, and the outer wall surface of the hollow fiber membrane and the outer tube are connected to each other. A gas-tight penetrator, feeding means for feeding the gas into the hollow portion of the hollow fiber membrane, an adsorber filled with an adsorbent, and a carrier passing through the outer tube to the adsorber. The apparatus includes a carrier gas supply unit for supplying gas, a heating control unit for heating and controlling the temperature of the adsorber, and a gas chromatograph for analyzing the gas desorbed from the adsorber.

A second high-speed chlorobenzene analyzing apparatus according to the present invention is the first high-speed chlorobenzene analyzing apparatus, wherein the hollow fiber membrane is made of silicone resin.

A third high-speed chlorobenzene analyzing apparatus according to the present invention is the first high-speed chlorobenzene analyzing apparatus, wherein the hollow fiber membrane is formed by coating a porous resin with a silicone resin.

A fourth high-speed chlorobenzene analyzing apparatus according to the present invention is the third high-speed chlorobenzene analyzing apparatus, wherein the silicon resin is dimethylpolysiloxane containing 0 to 50% by weight of diphenylsiloxane.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for separating and analyzing monochlorobenzene from other chlorobenzenes and chlorophenols was investigated and examined. A method for selectively collecting volatile compounds in a gas is described in J. Am. Chroma
togr. A Vol. 736 pp165-173
(1996), a selective separation is performed using a silicon resin hollow fiber membrane as described in (1996), and only the substance permeated through the hollow fiber membrane is collected with an activated carbon-based adsorbent.
There is a method in which the collected matter is desorbed by heating to ° C. and sent to a gas chromatograph.

The hollow fiber membrane made of a silicone resin has a characteristic that it does not transmit a highly polar substance such as moisture or a hardly volatile substance, but transmits only a low-polarity volatile substance. Here, selective separation of low-polarity volatile substances such as benzene, toluene, ethylbenzene, and trichlorethylene in exhaust gas has been achieved. In addition, the gas chromatograph device can complete the analysis in a short time (about 10 minutes) if only the volatile substance is used, and in this case, the analysis is completed in about 3 minutes.

One of the characteristics of monochlorobenzene is that, compared to other chlorobenzenes and chlorophenols,
It is a substance that is relatively volatile and has a lower polarity than water and the like.

Further, comparing the temperatures at which the vapor pressures of ethylbenzene and monochlorobenzene reach a vapor pressure of 20 mmHg, 38.6 ° C. and 35.3 ° C. respectively (Basic deviation II
The Chemical Society of Japan, pp. 715 and 717 (1975)
Year)), indicating that the degree of volatility determined from the vapor pressure curve is extremely close. Further, the interaction with the silicon resin can be estimated by using the elution time from the capillary column coated with the silicon resin used in the analysis of the gas chromatograph apparatus on the inner surface thereof.
As shown in the GC catalog of Company O, page 52, FIG. 101, the elution time of ethylbenzene and monochlorobenzene is short, and it can be seen that the interaction with silicon resin is very similar.

The temperatures at which dichlorobenzene and monochlorophenol reach a vapor pressure of 20 mmHg are 66.2 ° C. to 72.61 ° C. and 60.9 ° C. to 108.1 ° C., respectively.
(Chemical Handbook, Basic Part II, Chemical Society of Japan Part 718, pp. 714 (1975)) shows that it is less volatile than monochlorobenzene. Further, when the interaction between dichlorobenzene and the silicone resin was estimated using the elution time from the capillary column, it was found that SUPELCO G
As shown in the C product catalog, page 52, FIG. 101, it can be seen that dichlorobenzene has a longer elution time than monochlorobenzene and has a stronger interaction with the silicon resin.

According to the present invention, a permeator having a hollow fiber membrane made of silicon resin or the like is provided in front of an adsorption tube, and chlorobenzenes other than monochlorobenzene and chlorobenzenes are removed from the exhaust gas by passing the exhaust gas through the hollow portion of the hollow fiber membrane. This is based on the finding that selective collection is possible by allowing only a volatile substance such as monochlorobenzene to penetrate outside the hollow fiber membrane without allowing chlorophenols to penetrate outside the hollow fiber membrane.
The exhaust gas selectively permeated to the outside of the hollow fiber membrane is sent to an adsorption tube filled with an adsorbent and concentrated, and the adsorption tube is heated to, for example, 300 ° C.
And the exhaust gas concentrated in the adsorption tube is sent to a gas chromatograph for quantitative analysis.

As described above, by providing an infiltrator having a hollow fiber membrane made of a silicone resin or the like, it is possible to use a volatile compound such as chlorobenzenes and chlorophenols to which two or more substituents such as dichlorobenzene are added. Material is removed. As a result, only the volatile substance such as monochlorobenzene can be concentrated in the adsorbent in the adsorber. Monochlorobenzene is detected in the shortest time among chlorobenzenes and chlorophenols, so that the analysis time is shortened.

Further, since the volatile substances are removed by the penetrator, the volatile substances do not remain in the adsorption tube and the gas chromatograph apparatus, which adversely affects the measurement accuracy such as fluctuation of the baseline. Has no effect. In addition, since monochlorobenzene has a relatively high concentration, it is hardly affected by fluctuations in the baseline, and analysis with high measurement accuracy can be performed in a short time.

In the analysis of the present invention, if dust is contained in the exhaust gas, the pipe in the analyzer is clogged or contaminated, so that dust is removed from the exhaust gas sent into the analyzer as necessary. A vessel is provided. A general filter that can withstand exhaust gas components such as exhaust gas temperature and acid gas can be used for the dust remover.

The permeator has a double-tube structure consisting of a hollow fiber membrane made of silicon resin or the like through which exhaust gas passes, and an outer pipe surrounding the hollow fiber membrane. In the selective collection of monochlorobenzene, the shape of the hollow fiber membrane does not matter. In order to increase the permeation rate of monochlorobenzene, it is preferable that the length is as thin as possible and the length is as long as possible. Further, in order to increase the amount of monochlorobenzene collected from the exhaust gas, it is preferable to bundle a plurality of hollow fiber membranes and put them in an outer tube.

Instead of a hollow fiber membrane made of a silicone resin, a hollow fiber membrane obtained by applying a silicone resin such as polysiloxane to a porous resin such as polypropylene can be used.

Further, in order to allow the exhaust gas to enter from the hollow portion of the hollow fiber membrane and selectively permeate the exhaust gas into the outer tube, the outer tube is sealed by sealing between the outer tube at both ends of the outer tube and the side wall of the hollow fiber membrane. The pipe is made airtight, and an inlet and an outlet for the carrier gas are provided on the side wall of the outer pipe, and the exhaust gas permeated into the outer pipe is sent to the absorption pipe. The material of the outer tube is preferably a glass or metal tube that has been subjected to an inactivation treatment to prevent adsorption of monochlorobenzene.

The adsorbent was Carbotrap (SUPE)
A carbon-based adsorbent such as LCO (trade name) or a resin adsorbent such as Tenax (SUPELCO, trade name) can be used. The adsorption tube may be provided with a glass or metal tube that has been deactivated, and a heating control unit that can raise the temperature of this tube to about 300 ° C. In use, the heating temperature is set according to the characteristics of the adsorbent to be filled. 30 for Carbotrap
It can be heated to 0 ° C, and efficient desorption of adsorbate is possible. For heating, a heater or the like may be used. In order to shorten the analysis time and improve the detection sensitivity of the gas chromatograph, it is preferable to provide a Curie point pyrolyzer function capable of instantaneously raising the temperature to around 300 ° C.

In collecting the exhaust gas, in addition to the above, a pump and a gas flow meter as a feeding means for feeding the exhaust gas into the hollow portion of the hollow fiber membrane of the permeator, and a gas chromatograph through an adsorption tube and a carrier gas from an outer tube. What is necessary is just to have a carrier gas supply means for supplying to the chromatography apparatus.

The gas chromatograph device may be equipped with a normal capillary tube and has a function of raising the temperature to about 300 ° C. As the detector, a flame ionization detector, a mass spectrometer, or the like can be used in addition to the electron capture detector. The connection with the adsorption tube may be achieved by attaching a glass or metal tube that has been deactivated to the adsorption tube, and directly connecting to the capillary tube using a glass or metal connection part.

[0035]

[Embodiment 1] FIG. 1 is a configuration diagram showing a high-speed chlorobenzene analyzer according to one embodiment of the present invention. In the figure, 1 is an infiltrator in which a hollow fiber membrane 10 is housed in a glass outer tube 11, 2 is an adsorption tube filled with an adsorbent, 3 is a power supply for heating the adsorption tube 2, and 4 is an electron capture detector. The provided gas chromatograph apparatus, 5 is a helium gas cylinder for supplying a carrier gas (helium gas), 6 is a pump, 7 is a flow meter, 8 is a dust remover, 9 is an exhaust gas, and 12 is a carrier gas pipe.

The permeator 1 has 20 hollow fiber membranes 10 and the outer tube 1
The hollow fiber membrane 10 is a hollow fiber membrane made of silicone resin (inner diameter 0.03 mm, outer diameter 0.06 m).
m, wall thickness 15 μm, length 20 cm). Outer tube 11
Gas pipe 1 for sending out volatile substances
2 is installed and helium gas is helium cylinder 5
Supplied from

The adsorption tube 2 has an inner diameter of 0.53 mm and a length of 15 mm.
cm inactivated fused silica treated stainless steel tube,
Activated carbon based adsorbent (Product name: Car, manufactured by SUPELCO)
(botrap C) was used. The adsorption tube 2 is covered with a heating aluminum block, is supplied with a current from a power supply 3, and can be instantaneously heated to a temperature from room temperature to 300 ° C.

The gas chromatograph 4 is a GC-14.
The A type detector used was an electron capture type (manufactured by Shimadzu Corporation). The column for the gas chromatograph 4 is S
A DB-624 capillary column manufactured by UPELCO was used.

As the pump 6 for sucking the exhaust gas through the permeator 1, a diaphragm pump was used, and as the flow meter 7 for measuring the flow rate of the exhaust gas, an integrating pump was used. Further, a dust remover 8 is provided to remove dust in the exhaust gas.
Was placed in front of the permeator 1.

The analysis was performed according to the following procedure. The gas chromatograph device 4 supplies helium as a carrier gas from the helium cylinder 5 and enters a standby state. 20 ml of the waste gas 9 from the refuse incinerator is injected into the permeator 1 using the pump 6.
/ Min. At this time, the monochlorobenzene penetrates the hollow fiber membrane 10 made of silicon resin, is sent to the adsorption tube 2 by the carrier gas, and is collected. At this time, the temperature of the adsorption tube 2 was room temperature. As a result, chlorobenzenes and chlorophenols other than monochlorobenzene do not permeate through the silicone resin hollow fiber membrane 10 and are exhausted together with the exhaust gas 9.

When the exhaust gas 9 was sucked for 3 minutes,
Is instantaneously heated from room temperature to 300 ° C. for about 10 seconds.
00 ° C was maintained. At this time, the monochlorobenzene collected by the adsorption tube 2 is desorbed and sent to the gas chromatograph device 4. The time for these collection and desorption is about 3 minutes.

The gas chromatograph device 4 always has 100
C. was maintained.

FIG. 2 shows an analysis result (chromatogram) of monochlorobenzene measured by a gas chromatograph. No peaks of chlorobenzenes and chlorophenols other than the monochlorobenzene peak P1 are observed. The other peaks in FIG. 2 are peaks of hydrocarbon-based substances such as toluene contained in exhaust gas other than chlorobenzenes and chlorophenols. This shows that chlorobenzenes and chlorophenols, which are less volatile than monochlorobenzene, have been removed by the permeator 1.

In FIG. 2, the peak P1 of monochlorobenzene is detected within about 3 minutes. Therefore, it can be seen that the analysis time by the gas chromatograph apparatus is sufficient within 3 minutes. Here, since the gas chromatograph apparatus is always kept at 100 ° C., a temperature lowering operation is unnecessary.

Since no exhaust gas remains in the adsorption tube 2, the monochromobenzene can be newly collected in the adsorption tube 2 at the same time as the measurement by the gas chromatograph device is performed. Upon completion of the measurement, the adsorption tube 2 was rapidly heated to 300 ° C.
The following measurements can be performed.

Embodiment 2 FIG. The overall configuration of the exhaust gas analyzer used for analysis is the same as that of the first embodiment. The difference from Example 1 is that a hollow fiber membrane obtained by applying dimethylpolysiloxane to a hollow portion of a hollow body of a polypropylene resin was used.

FIG. 3 is a configuration diagram of the hollow fiber membrane 10 used in the permeator 1. The hollow fiber membrane 10 is composed of a polypropylene resin membrane (inner diameter 0.03 mm, length 20 cm) 14 on which dimethylpolysiloxane 13 is applied at 1 μm.

FIG. 4 shows a chromatogram measured in the same procedure as in Example 1. As in FIG. 2, a peak of only monochlorobenzene was detected, and non-volatile chlorobenzenes and chlorophenols other than monochlorobenzene were not detected, indicating that they were removed by the permeator 1.

Table 1 shows a comparison between the case where the hollow fiber membrane made of silicone resin of Example 1 was used and the signal intensity of monochlorobenzene of Example 2.

[0050]

[Table 1]

As is evident from Table 1, the signal intensity is higher in the case of the hollow fiber membrane coated with dimethylpolysiloxane 13 of the present Example 2. This is presumably because the permeation of monochlorobenzene was completed in a short time because the thickness of the applied dimethylpolysiloxane was as thin as 1 μm as compared with the thickness of the hollow fiber membrane made of silicone resin of 15 μm.

Embodiment 3 FIG. In the hollow portion of the polypropylene resin, 0 to 50% by weight of diphenylpolysiloxane to dimethylpolysiloxane (0, 5, 10, 20, 35, 50
(% By weight) were applied to form a hollow fiber membrane similar to that in Example 2, and the signal intensity of monochlorobenzene was compared.

FIG. 5 is a chromatogram showing the results of analysis using a hollow fiber membrane coated with 50% diphenylpolysiloxane-50% dimethylpolysiloxane. As shown in the figure, the peak P of monochlorobenzene
In addition to the peak 1, the peak P2 of monochlorophenol and the peak P3 of dichlorobenzene were detected, but within the allowable range. It is considered that P2 and P3 were detected because the polarity of the applied polysiloxane increased as the ratio of diphenylpolysiloxane increased, and the polar substance permeated the hollow fiber membrane. When a hollow fiber membrane coated with dimethylpolysiloxane containing 0 to 35% by weight of diphenylpolysiloxane is used, only the peak of monochlorobenzene is detected, and in the infiltrator 1, hardly volatile chlorobenzenes and chlorophenols other than monochlorobenzene are detected. The species were found to have been removed.

Table 2 shows a comparison of the signal intensity of monochlorobenzene when using a hollow fiber membrane coated with each polysiloxane.
Shown in

[0055]

[Table 2]

The monochlorobenzene having the highest signal intensity was the hollow fiber membrane coated with 5% diphenylpolysiloxane-95% dimethylpolysiloxane. This is considered to be due to the fact that monochlorobenzene is slightly polar.

In the above Examples 2 and 3, the case where a polypropylene resin is used as the resin to which the polysiloxane is applied is shown, but other porous resins can be used.

Comparative example. The permeator 1 was not provided in the preceding stage of the adsorber 2, and other than that, using the same apparatus as in Example 1, FIG.
The same test was performed as when the result of the above was obtained. FIG. 6 shows the obtained chromatogram. In this case, a peak other than the monochlorobenzene peak P1 is observed, and monochlorophenol P2, dichlorobenzene P3, and trichlorobenzene P4 are recognized.

In this case, chlorobenzenes and chlorophenols other than monochlorobenzene are collected in the adsorption tube 2 and sent to the gas chromatograph device 4. Therefore, if the analysis time is 3 minutes, the non-volatile substances remain in the apparatus, which adversely affects the subsequent measurements. That is, the baseline fluctuation of the chromatogram cannot be avoided.

[0060]

According to the method for high-speed analysis of chlorobenzene according to the present invention, gas is passed through the hollow portion of the hollow fiber membrane, and chlorobenzene in the gas is selectively permeated outside the hollow fiber membrane. After the chlorobenzene selectively permeated is collected by the adsorbent, the chlorobenzene is heated and desorbed from the adsorbent and measured by a gas chromatograph, so that only monochlorobenzene can be analyzed, and the analysis time is shortened. In addition, since non-volatile substances do not remain in the analyzer, measurement accuracy does not decrease due to fluctuations in the baseline of the gas chromatogram.

According to the first and second chlorobenzene high-speed analyzers according to the present invention, the hollow fiber membrane is housed in the outer tube, and the permeation is made airtight between the outer wall surface of the hollow fiber membrane and the outer tube. Device, a feeding means for feeding gas into the hollow portion of the hollow fiber membrane, an adsorber filled with an adsorbent, and a carrier gas supply means for supplying a carrier gas to the adsorber through the outer tube. Since it has a heating control means for heating and controlling the temperature of the adsorber and a gas chromatograph device for analyzing the gas desorbed from the adsorber, only monochlorobenzene can be analyzed, and the analysis time can be improved. In addition, since non-volatile substances do not remain in the analyzer, measurement accuracy does not decrease due to fluctuations in the baseline of the gas chromatogram.

As the temperature control in the analyzer, only a heating control means for controlling the temperature of the adsorption tube may be provided, and the gas flow path in the analyzer may be changed during continuous measurement. There is no need to provide a simple valve switching mechanism or the like, and an extremely simple device configuration can be achieved.

According to the third and fourth chlorobenzene high-speed analyzers of the present invention, the thickness of the hollow fiber membrane is freely set since the hollow fiber membrane is formed by coating a porous resin with a silicone resin. It is possible to increase the signal intensity of monochlorobenzene by thinning.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing an apparatus for analyzing chlorobenzene according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a chromatogram measured by the analyzer according to the first embodiment of the present invention.

FIG. 3 is a perspective view showing a structure of a hollow fiber membrane used in an analyzer according to a second embodiment of the present invention.

FIG. 4 is a diagram showing a chromatogram measured by the analyzer according to the second embodiment of the present invention.

FIG. 5 is a diagram showing a chromatogram measured by the analyzer according to the third embodiment of the present invention.

FIG. 6 is a diagram showing a chromatogram measured as a comparative example with the present invention.

[Explanation of symbols]

1 infiltrator, 2 adsorber, 3 power supply, 4 gas chromatograph, 5 helium cylinder, 6 pump, 7 flow meter, 8 dust remover, 9 exhaust gas, 10 hollow fiber membrane, 11
Outer pipe, 12 Carrier gas pipe, 13 Dimethyl polysiloxane, 14 Polypropylene resin, P1 monochlorobenzene, P2 monochlorophenol, P3 dichlorobenzene, P4 trichlorobenzene.

Claims (5)

[Claims] 1. An analysis method for analyzing chlorobenzene in a gas, wherein the gas is passed through a hollow portion of a hollow fiber membrane, and chlorobenzene in the gas is selectively permeated outside the hollow fiber membrane, A method for high-speed analysis of chlorobenzene in which the selectively permeated chlorobenzene is collected by an adsorbent, and then the chlorobenzene is desorbed by heating from the adsorbent and measured by a gas chromatograph. 2. An analyzer for analyzing chlorobenzene in a gas, comprising: a penetrator in which a hollow fiber membrane is housed in an outer tube and an airtight state is provided between the outer wall surface of the hollow fiber membrane and the outer tube; Feeding means for feeding a gas into the hollow portion of the hollow fiber membrane, an adsorber filled with an adsorbent, carrier gas supplying means for supplying a carrier gas to the adsorber through the outer tube, A high-speed chlorobenzene analyzer comprising a heating control means for heating and controlling the temperature of the vessel, and a gas chromatograph apparatus for analyzing the gas desorbed from the adsorber. 3. The high-speed analyzer for chlorobenzene according to claim 2, wherein the hollow fiber membrane is made of a silicone resin. 4. The chlorobenzene high-speed analyzer according to claim 2, wherein the hollow fiber membrane is formed by applying a silicon-based resin to a porous resin. 5. The high-speed chlorobenzene analyzer according to claim 4, wherein the silicon resin is dimethylpolysiloxane containing 0 to 50% by weight of diphenylsiloxane.