JPH11344477A - Method and device for monitoring waste water of decomposition treatment device for hazardous organic substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To directly measure hazardous substances, etc., in waste water actually discharged from an organic hazardous substance decomposition and treatment device and control the waste water based on the information obtained by the measurement by connecting a quantitative specimen collecting device, a solid-phase extractor, and a chromatograph to a waste water line in an on-line state. SOLUTION: The waste water from a decomposing and treating unit is sent to a sample collecting section 10 as a liquid sample and the section 10 stores a fixed amount of sample in a calibration loop 18. Then methanol is made to flow to an automatic cartridge supplying device 40 through a concentration and refinement introducing section 30 by operating a solvent change-over valve 21 and discharged to a drain 32 after the methanol removing stains from a solid-phase cartridge 41. Then the methanol in the cartridge 41 is replaced with water by making the water to flow by operating the valve 21. After the methanol in the cartridge 41 is replaced with the water, the sample stored in the calibration loop 18 is sent to the cartridge 41 and hazardous organic substances are collected and concentrated. The concentrated component is eluted and the eluate is detected by introducing the eluate to a chromatograph 50. Then the obtained data are processed and the instructive information for the discharge, storage, and retreatment of the treated water is transmitted by feeding back the information on the processed data.

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 monitoring waste water from an apparatus for decomposing harmful organic substances by a supercritical water oxidation method, an alkali hydrolysis method or the like.

[0002]

2. Description of the Related Art The treatment of hazardous wastes such as PCBs requires closed treatment in addition to complete decomposition. Decomposition treatment of harmful organic substances by the supercritical water oxidation method is excellent in this respect, and it has been drawing attention, but since treated water containing substances after the reaction is drained, the remaining amount or concentration of harmful organic substances is subject to administrative standards. It is necessary to measure whether it is below the value. Conventionally, monitoring devices for drainage plants include spectrophotometers,
Various devices such as a chemiluminescence photometer and a pH meter are used.

[0003] Further, in the decomposition treatment of harmful organic substances by the supercritical water oxidation method, an apparatus provided with a safety stop circuit for closing a discharge flow path and returning to a preheater through a branch flow path, and using the apparatus, There has been proposed a method of measuring the temperature and pressure of a reaction vessel for performing a decomposition treatment, the flow rate ratio between an oxygen-containing fluid and a harmful organic substance, and operating the apparatus based on the measured values.
(Japanese Unexamined Patent Publication No. Hei 7-275872)

[0004]

However, in the conventional monitoring apparatus for a drainage plant, for example, harmful organic substances such as PCBs have low drainage standard values and are almost impossible to measure. Taking PCB as an example, in a general measurement method, as represented by JIS-K0093, sampling-liquid phase extraction (or solid phase extraction) -cleanup-concentration-gas chromatograph (or GC-) with an electron capture detector MS), and many other steps are required. For this purpose, a large drainage reservoir is required for the decomposition treatment apparatus, which is not practical.

Further, in the above invention, it is possible to know indirectly the condition of the apparatus by the temperature and pressure of the decomposition apparatus and the flow ratio of the oxidizing agent-containing fluid and the harmful organic substance. It is impossible to know whether the processing liquid has been discharged. Therefore, when a harmful substance is present in the treated wastewater, there is a risk that the harmful substance may return to the natural environment as it is, which is dangerous.

[0006]

Accordingly, in the present invention, various kinds of information in a decomposition solution discharged in the decomposition treatment of harmful organic substances are quickly captured, and a rapid measurement is performed to guarantee the safety of the decomposition solution. A solid-phase extraction device for solid-phase extraction of trace amounts of harmful substances from the collection line, and a solid-phase extraction system. The on-line connection is made to a chromatograph for analyzing and processing the above components.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to a supercritical water splitting apparatus shown in the drawings. Reference numeral 1 denotes a supercritical water decomposition apparatus, which includes a decomposition processing unit 2 and a gas-liquid separator 3, and is configured to be drained from a valve 4 through a water distribution pipe 5. The supercritical water decomposition apparatus 1 has a
No. 532 and other publications are widely known.
The apparatus reacts a mixture of an organic substance, a gas containing water and oxygen, and an oxidizing agent such as hydrogen peroxide in a uniform liquid phase at a temperature of 374 ° C. or more and a pressure of 22 MPa or more to oxidize and decompose the organic substance. Things.

[0008] The constitution is such that an organic substance-containing liquid (water) as an object to be treated and an oxidizing agent solution are respectively sent to a preheater under pressure, and then heated in a high-pressure reactor to reach the supercritical condition. You. The mixture (fluid) that has entered the high-pressure reactor heats up due to the oxidation reaction of the organic matter, and the organic matter becomes mainly carbon dioxide and water, and the hetero atoms in the organic matter →
It becomes acid, salt and chloride. For example, when the decomposition target is PCB, it is carbon dioxide + water + chlorine (inorganic salt).

For discharging the reaction product, a method using a gas-liquid separator is generally used. The treated wastewater accompanying the exhaust gas enters the gas-liquid separator 3 through the discharge pipe 6, and the treated wastewater is discharged out of the system through the discharge pipe 5.
To drain more. The target harmful organic substances are PC
There are various types such as B, dioxin, pesticides, especially highly toxic pesticides such as BHC and CNP.

Reference numeral 10 denotes a sampling section, for example, a sampling pipe 12 is connected to a drain pipe 5 and connected to a pump 14 via a valve 17 and a filter 13.
Communicates with the communication hole 151 of the valve 15. Valve 1
5 is provided with a calibration loop 18 between the communication holes 152 and 155, and the communication hole 156 is provided with a return pipe 19 to the gas-liquid separator 3.

Reference numeral 20 denotes a solvent supply unit for performing various cleaning and feeding operations by supplying various solvents.
As an example, the solvent switching valve 21 is used, and the through hole 21 is used.
1, for example, dichloromethane, methanol in the through hole 212, water in the through hole 213, acetonitrile / water and the like in the through hole 214, respectively.
The valve 15 communicates with the communication hole 154 of the valve 15 through the second hole 2. The communication hole 153 of the valve 15 communicates with the communication hole 311 of the six-way valve 31 of the concentration / purification introduction unit 30.
As the sample collection unit 10, there are various methods other than the method using the calibration loop 18 as described above.

The concentration / purification introduction unit 30 concentrates and purifies the sample collected by the sample collection unit 10 and performs gas chromatography,
It has a function of sending it to an analyzer 50 such as a liquid chromatograph. One specific example is the six-way valve 31.
Through hole 311 communicates with the communication hole 153 of the valve 15,
The communication hole 312 communicates with the drain 32. Communication hole 3
13 and the communication holes 316, the solid-phase cartridges 41, 4
An automatic cartridge supply device 40 for automatically supplying and clamping 1,... Is provided. The automatic cartridge supply device 40 automatically moves the solid-phase cartridge 41 between the clamp portions 42, 42 by automatically moving the holder in which many solid-phase cartridges 41 are arranged in parallel.
Clamp between two. By forming another clamp portion, the solid-phase cartridge 41 can also be manually clamped. As for the movement of the holder, it is possible to use a known serial type or turntable type.

[0013] As a trapping agent, the main component of the discharged liquid is water, the combustion products after oxidation (hereinafter referred to as "combustion") decomposition become inorganic, and the intermediates during combustion are also extremely oxidized. Focusing on high polarity and water solubility, select the type according to the properties of the target substance. For example, when the target substance is a polycyclic aromatic compound such as phenols and naphthalene designated as environmental pollutants in environmental water, a solid phase cartridge 41 composed of a benzenedivinylbenzene polymer is used. Collect and concentrate. In the case of ionic surfactants such as alkyl sulfates, a solid-phase cartridge of an ion exchange resin is used, and in the case of a trace drug in blood, an octyl group or an octadecyl group is used.
A so-called reverse phase solid phase cartridge in which a phenyl group or the like is bonded to silica gel or a polymer material is used. The shape of the solid phase cartridge is, for example, an inner diameter of 1 to 6 mm,
A pipe having a length of 1 to 30 mm and a filler of 2 to 100 microns is used. A disk-shaped collecting material in which the filler is fixed with Teflon or glass fiber may be used by using an adapter.

When a liquid chromatograph is used as the chromatograph, a liquid chromatograph pump 52 connected to the eluent 51 is connected to a communication hole 315 of the six-way valve 31. The communication hole 314 communicates with the data processing unit 60 through a liquid chromatograph 50 including a separation column 53, a detector 54, and the like.

Next, the operation will be described. The discharge discharged from the decomposition processing unit 2 is supplied to the gas-liquid separator 3.
And a sample of the liquid is sent from the discharge pipe 5 to the sample collection unit 10 via the collection pipe 12. Sampling unit 1
The sample sent to 0 is returned from the communication hole 151 of the valve 15 through the communication hole 152 through the calibration loop 18 to the gas-liquid separator 3 through the return pipe 19. In this way, a fixed amount of sample is accumulated in the calibration loop 18.

Next, the through holes 2 are formed by the solvent switching valve 21.
12 is selected, and methanol is caused to flow from the communication hole 210 by the pump 22. At that time, the methanol enters the concentration / purification introduction section 30 through the communication holes 154 and 153 of the valve 15. At this time, the switching of the six-way valve 31 causes the communication hole 3
11 and 316 communicate with each other, and methanol enters the automatic cartridge supply device 40 through the communication hole 316 to remove dirt from the clamped and set solid phase cartridge 41 and at the same time to release air, thereby facilitating compatibility with water. Then, the water is discharged to the drain 32 through the communication holes 313 and 312 of the six-way valve 31.

Next, similarly, water is flowed by switching the solvent switching valve 21 to replace methanol in the solid phase cartridge with water. Then, the valve 15 is switched, and the calibration loop 18
Is sent to the solid phase cartridge 41. Here, organic harmful substances are collected / concentrated in the solid phase cartridge 41. By switching the solvent switching valve 21, an appropriate mixed solution such as acetonitrile / water is sent,
Wash away any water-soluble interfering substances in it.

Next, the six-way valve 31 is switched to elute the components concentrated in the solid phase cartridge 41 and introduce them into the liquid chromatograph 50. At this time, the eluted components are separated by the separation column 53, detected by the detector 54, sent to the data processing device 60, and subjected to data processing.
By the data processing, this information is fed back to determine the release, storage, and reprocessing of the treated water, and transmit the respective instruction information to the supercritical water decomposition treatment apparatus 1. At that time, in order to efficiently send the concentrated sample to the solid phase cartridge,
It is recommended to take a backflush method. In this method, the eluent 51 is connected to the communication hole 314 of the six-way valve 31 via the liquid chromatography pump 52,
3 is connected to the communication hole 315 and the concentrated sample in the solid phase cartridge is sent to the separation column.

Another example of the sampling section 10 will be described with reference to FIG. Return pipe 19 from pump 14 in FIG.
A branch pipe 191 is provided on the way to, and communicates with the solvent switching valve 21 via the filter 192. The communication pipe 21
0 is connected to the 6-way valve 31 via the constant flow pump 221. Other than the above, the six-way valve 31, the cartridge automatic supply device 40, and the liquid chromatograph 50 of FIG.
Is the same. In such an apparatus, the sample is directly introduced into the solvent switching valve 21, and the amount of concentration is determined by setting the capacity and the operation time of the constant flow pump 221. This is convenient for mass concentration.

The gas chromatograph 50 of the sample shown in FIG.
The apparatus shown in FIG. 4 shows a method using a solvent vaporization column. The communication hole 315 of the six-way valve 31 is connected to the communication hole 71 of the valve 70. A solvent 76 is connected to the through-hole 72 via a microfluidic pump 75. The through hole 73 is connected to the solvent 76, and the through hole 74 is connected to the carrier gas 78. Communication hole 79
Is connected to a resistance tube 791 of the same size as the column of the gas chromatograph 50.

The gas chromatograph 50 has a solvent vaporization column 501 and a re-holding column 502, communicates with a main column 504 via an outlet 503, and then a detector 505.
, And the result is sent to the data processing unit 60.

This operation will be described. In order to elute the components to be analyzed collected in the solid phase cartridge 41 and transport them to the capillary column as the main column 504 for separation, several tens to several hundreds of solvents are required. When all of this large amount of solvent is fed into the capillary column, various problems occur. For this purpose, it is vaporized at the entrance of the capillary column. That is, the solvent is sent to the six-way valve 31 through the through-holes 72 and 71 of the valve 70 by the operation of the small amount liquid sending pump 75. At that time, the solvent passes through the communication holes 315 and 316 and reaches the solid phase cartridge 41, where the component to be analyzed is eluted and sent to the gas chromatograph 50 through the communication holes 313 and 314. Then, the solvent is vaporized in the solvent vaporization column 501, and the valve 70 for discharging the solvent from the discharge port 503 is switched, so that the carrier gas through hole 74,
The communication holes 315 and 31 of the six-way valve 31 through the same 71
Then, it is sent to the gas chromatograph 50 via 4. Therefore, the analysis target component held in the re-holding column 502 is
It is conveyed to the capillary column 504 as a main column. Then, it is detected by the detector 505.

At this time, it is recommended to flow a purge gas such as nitrogen or helium in order to dry the water in the solid phase cartridge 41. As an example of this, the valve 80
The purge gas is communicated with the communication hole 83, and the communication hole 82 is communicated with the communication hole 311 of the six-way valve 31. The communication hole 81 is provided with the communication hole 15 of the six-way valve 15.
It is connected to 3. With such a mechanism, the solid phase cartridge 41 is dried.

Based on the analysis of the chromatograph 50, the data is processed by the data processing unit 60. For example, when PCB is used as the object, the PCB decomposition rate (%), the dechlorination rate (%), the TO
The C decomposition rate (%) is calculated, and this processing information is fed back to the control unit of the decomposition processing apparatus in accordance with safety standards.
For example, the processing temperature, the processing pressure, the supply flow rate of the target component (per hour), the SCW / PCB flow rate ratio, and the air ratio (the amount of air required to theoretically oxidize and decompose the supplied PCB waste liquid to 100%) The operation of the decomposer is followed by reviewing each condition such as the ratio of

[0025]

According to the present invention as described above, a quantitative sample collection device and a solid phase extraction device for solid phase extraction of a trace amount of harmful substances from the collection donor are provided in a drain line of a toxic organic substance decomposition treatment device. The on-line connection with the chromatograph for analyzing and processing the above phase-extracted components enables the target substances and harmful substances in the wastewater to be measured directly by the decomposition treatment liquid that is actually discharged. Control including discharge stop can be performed, and the return of harmful substances to the natural environment can be prevented. In addition, the operation status of the disassembly processing device can be controlled based on the measurement information, and the operation process satisfying the safety standards can be performed. Of course, they can take an immediate response in response to changes over time, and can ensure safety.

[Brief description of the drawings]

FIG. 1 is a schematic flow chart of one embodiment of the present invention.

FIG. 2 is an explanatory diagram of a main circuit of the above.

FIG. 3 is an explanatory view of a main part of another embodiment.

FIG. 4 is a schematic explanatory view of an example of use of the gas chromatograph of the above.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Supercritical water decomposition apparatus 2 Decomposition processing unit 3 Gas-liquid separator 4 Valve 5 Drain pipe 6 Discharge pipe 7 Exhaust gas pipe 10 Sampling section 20 Solvent supply section 30 Concentration introduction section

Continued on the front page (72) Inventor Tomoyuki Iwamori 1-2-8 Shinsuna, Koto-ku, Tokyo Organo Corporation (72) Inventor Masakazu Takahashi 237-2 Sayamagahara, Iruma City, Saitama Prefecture Inside the Musashi Factory (72) Inventor Yoshiaki Furusho 237-2 Sayamagahara, Iruma City, Saitama Prefecture G Musashi Factory

Claims (3)

[Claims] 1. A sample collection device, an extraction device for extracting and concentrating a trace amount of harmful substances from the collected sample, and a chromatograph for analyzing and processing the extracted components in a drain line of a toxic organic substance decomposition treatment device. A wastewater monitoring device for a harmful organic substance decomposition treatment device, which is connected online. 2. The effluent monitoring device according to claim 1, wherein the extraction device sequentially brings the solid phase cartridge to the sample supply device so that the sample can be supplied. 3. A sample is collected from the wastewater after the decomposition treatment of the harmful organic substance, a trace amount of the harmful substance is concentrated by a solid phase extraction method, and this is eluted and introduced into a chromatograph. Calculate the decomposition rate of harmful organic substances based on the group,
A method for monitoring effluent of harmful organic substances, wherein the method is compared with the processing status of the decomposition processing apparatus and reflected in the processing status of the decomposition processing apparatus.