JP2001038101A - Extraction using supercritical fluid as solvent and cleaning method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To perform extraction by connecting to an analyzer for an ultra trace component on line. SOLUTION: In this extracting method, a reboiler 3 for heating super critical fluid filled from a filling port arranged in an adequate part of a vertically structured supercritical fluid circulation pipe line 2 to lower the density and a super heater 4 for further heating to increase the density gradient are arranged respectively in a lower part of one of vertical passages 2a of the pipe line 2 and in the upper position thereof, a sample filling vessel 12 made from a mesh body and a cooler 15 for cooling the fluid to increase the density are arranged respectively in the midway of another vertical passage 2b and in the upper position thereof and further a super cooler 17 for accelerating the increase of the density of the fluid in the lower part of the pipe line 2 is arranged in the bottom of the pipe line 2. The solvent is circulated automatically by utilizing the difference of the density generated by the heating and the cooling as driving force, the extraction enough for an object to be analyzed is performed by repeating the contact of the same solvent with the sample by the circulation and the sampling from an adequate part of the pipe line is carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an extraction and washing system using a supercritical fluid as a solvent.

[0002]

2. Description of the Related Art A fluid in a subcritical or supercritical state is a fluid at or near a critical temperature and a critical pressure, and has a density close to a liquid and a large diffusion coefficient close to a gaseous substance ( Hereinafter, in the present application, the above-mentioned fluid is generically referred to as “supercritical fluid”.) Because of this property, various compounds can be extracted quickly and efficiently in large quantities. Further, since the dissolving ability for various compounds is greatly changed by slightly changing the pressure and the temperature, there is also a feature that selective extraction can be performed.

[0003] The excellent extraction capability of supercritical fluids enables the analysis of trace components, and the ability to connect the extraction solvent to analytical equipment (gas, liquid, supercritical fluid chromatograph, etc.) on-line is rapid. Analysis is realized.

Conventional extraction using a supercritical fluid as a solvent is described in, for example, JP-A-61-183395 and JP-A-63-863.
As disclosed in Japanese Patent No. 3198, etc., a one-batch, one-through system is used in which a predetermined solvent is charged from a cylinder via a compressor and a heat exchanger into an extraction column in which a sample in a pressure-resistant chamber is allowed to stand and is brought into contact with the sample. .

[0005] The extraction system in the analyzer is compact due to the nature of the device, is configured to be able to extract and analyze with a small amount of sample, and each device is designed to be much smaller than in a mass production facility. Have been.

[0006]

In the above-mentioned extraction system in which the solvent has a one-time chance of contacting the sample with the solvent, no matter how excellent the supercritical fluid extraction ability is, the solubility is excessively low. In the case of a so-called ultra trace component having a small content in a sample, it is impossible to obtain a sample having a concentration that can be analyzed.

In such a case, first, additional solvent is added or the sample is renewed in order to increase the amount of extraction. However, since the concentration in the obtained extract is not particularly increased, an extremely troublesome concentration step is inevitable. It is impossible to put it into the analyzer until after passing through.

However, as a practical problem, frequent replacement of cylinders and compressors for a long time, security in operation of heat exchangers (for high-pressure equipment), line stoppage at every sample renewal,
Cautionary work on restarting (requires pressure reduction and high pressure setting)
Too harsh.

The present invention has been made in view of the circumstances described above, and has as its object to set up a separate line for adding an additional solvent, renewing a sample, and concentrating even a very small amount of components. It is an object of the present invention to provide an extraction system using a supercritical fluid as a solvent, which eliminates the need for extraction of a desired concentration in a much shorter time and enables reliable online connection with an analytical instrument. When the solvent in the extraction system is a subcritical liquid, it is used for washing. Therefore, the title of the present invention is an extraction and washing system.

[0010]

In order to achieve the above-mentioned object, an extraction and washing system using a supercritical fluid as a solvent according to the present invention comprises: In addition, a reboiler comprising an external contact device for heating a supercritical fluid, which is condensed at room temperature at a filling temperature from a filling port disposed at an appropriate position in the pipe line to reduce the density, and further heating the reboiler to a higher density gradient A superheater consisting of an external contact device for increasing the temperature is arranged, and a sample filling container made of a mesh body is arranged in the middle of the other vertical path, and the reboiler and the superheater are heated and the other vertical path is heated. The solvent is automatically circulated using the density difference generated by cooling at room temperature as a driving force, allowing extraction that can be analyzed by repeated contact of the same solvent with the sample by the circulation, and sampling from an appropriate part of the above-mentioned conduit. Those were suppose.

External contact for lowering the density by heating a filled supercritical fluid through a filling port provided at an appropriate position in one vertical portion of a vertical supercritical fluid circulation pipe A superheater consisting of an external contact device for increasing the density gradient by further heating is arranged on the reboiler consisting of the device and the upper part, and a sample filling container consisting of a mesh body and the fluid on the upper part are placed in the middle of the other longitudinal path. The reboiler further comprises a cooler comprising an external contact device for cooling and increasing the density, and further comprising a supercooler comprising an external contact device at the lower portion of the pipeline to promote the higher density of the lower portion of the pipeline. And the solvent is automatically circulated as a driving force by the heating of the superheater and the density difference generated by the cooler in the other vertical path and the supercooler at the bottom, and by repeated contact of the same solvent with the sample by the circulation. Analysis To enable or obtain extract is obtained by the sampling from the appropriate sites of the conduit.

[0012]

[Function] The fluid (solvent) filled in the closed circulation line is
Boiling due to heating increases the pressure, lowers the density, and rises in the tube.

Next, the sample is condensed and densified by cooling, descends in the tube, and passes through a solid sample to extract a target component. The fluid automatically continues to circulate in the circulation line using the density difference generated by heating and cooling as a driving force. Such repeated contact of the same sample with the same solvent leads to crystallization (which can occur when the density is reduced by heating) upon concentration, and increases the concentration of the trace component to a concentration that can be analyzed. .

Thus, there is no need to add an additional solvent, update the sample, or set up a separate line for concentration, and it is possible to extract a desired concentration in a much shorter time and to use a straightforward analytical instrument. There is provided an extraction and washing system using a supercritical fluid as a solvent to enable online connection with the system.

Further, after the fluid has been filled to a predetermined density, the system determines the required conditions and circulation amount for the desired pressure and temperature (both are monitored) for heating, superheating, cooling and supercooling. Because it can be set, researchers can work under the conditions necessary to achieve their goals.

For example, a certain chemical substance is greatly changed by changing the solubility temperature and pressure in supercritical carbon dioxide. As an example, the solubility of naphthalene in supercritical carbon dioxide is 15 w
At 0 atmosphere and 35 degrees, it drops to 2.5 w%. If the pressure is kept constant and the temperature is changed, the solubility may change significantly. In the case of naphthalene, the solubility in supercritical carbon dioxide at 90 atm 40 ° C is 2.5 w%, but at 90 atm 50 ° C it is 0.6 w%.
Becomes As described above, setting the temperature and pressure is extremely important for improving the extraction effect, and the extraction system must be able to operate under conditions set according to the researcher's intention, but this system can respond to this. .

The present system has a pipeline structure, and can be made to have excellent pressure resistance by adopting a high-pressure pipe. The temperature (−80 ° C. to 1,000 ° C.) and the pressure (0.1 atm. To 10,000) are independent of the type of the solvent.
Pressure) operating conditions.

In the main equipment of the present invention, the external contact equipment avoids the burden of pressure resistance, and the equipment requiring a pressure resistance design uses the high-pressure pipe for the pressure-resistant frame to reduce the design burden. Can be reduced.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to FIG.

FIG. 1 shows the basic configuration of the present system. In the drawing, reference numeral 1 denotes a small cabinet accommodating a supercritical fluid circulation high-pressure pipe 2 of a vertical configuration according to the present invention. This shows the possibility of small-scale configuration of the system of the present invention.

Main equipment is installed in the cabinet 1. First, a reboiler 3 of an external contact device is disposed below one of the longitudinal paths 2a, and a superheater 4 of the external contact device is disposed above the reboiler 3, and the respective heating elements 3a and 4a are connected to temperature controllers 5 and 6, respectively. Have been.

Further, thermocouples 7 and 8 are attached to the reboiler 3 and the superheater 4, respectively. An electric sensor 9 for detecting the system pressure is arranged at the upper part of the pipe 2 and is monitored by a measuring instrument 10, and a safe operating pressure is managed by a rupturable plate 11 arranged nearby. I have.

A sample filling container 12 (extraction column) made of a mesh body made of stainless steel or the like that can withstand high temperature and high pressure is disposed in the middle of the other vertical path 2b. A thermocouple 13 is provided in the extraction column. A cooler 15 composed of an external contact device connected to the cooling unit 14 is arranged above the extraction column. Further, a supercooler 17 composed of an external contact device connected to a cooling unit 16 is disposed below the pipeline 2 located in front of the reboiler 3.

The above-mentioned cooler 15 and supercooler 17 are unnecessary when the solvent condenses at room temperature. That is, as a minimum arrangement, it is possible to operate with only the reboiler 3 and the superheater 4. However, in this case, the flow occurs naturally,
The balance between the amount of heating to the system and the heat loss in the circulation of the system will also result in a gradual increase in system temperature and pressure.

A sampling valve 1 is provided below the pipe 2.
An analysis tube 20 having 8 and 19 is provided. In the illustrated example, a solvent filling port 21 is provided below the extraction column, and a thermocouple 22 is provided downstream. The above-mentioned system can give a calculated flow rate to the pipeline 2 by controlling the heating and cooling by the computer 23 using the temperature and pressure data from the various instruments described above. The computer 2
3 is desirable to have a keyboard, monitor, and pointing device, because the display of input data and the progress of the experiment can be grasped.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The manner of carrying out the present invention under various high pressures will be described below.

FIG. 2 shows a case of extraction at a high temperature under a pressure of 400 atm. The sample filling container 12 has a length of 50 to 200 mm, an outer diameter of up to 25.4 mm, and an inner diameter of up to 14 mm. The reboiler 3 is desirably of the same size as the vessel 12, and is preferably installed at a lower position so as to increase the fluid momentum caused by the density gradient due to the thermal gradient. Line 2 is a reboiler 3,
It is desirable to manufacture the durable material such as stainless steel including the superheater 4 and fittings, elbows and tee joints.

In the present invention, in the case of pressure operation up to 400 atm, the multi-way valve 24 is used for sampling, which is used not only for taking out a sample, but also for high performance liquid chromatography, supercritical chromatography,
Used as an interface to connect to gas chromatography and other analytical instruments (Figure b). Each of the multi-way valves 24 has six inlets and outlets from which a sample can be taken out.
It is desirable that the fluid in the entire system is not affected at the time of sample removal.

In the case of a temperature of 600 ° C. and an atmospheric pressure of 400 atm, the following configuration is desirable.

The heater is of an electric type, and 200 for the reboiler 3.
Although it is desirable that the superheater 4 has a capacity of about 200 to 2,000 W, a heater having a larger capacity is selected depending on the size and circulation amount of the system. The size of reboiler 3 is container 1
A size equivalent to 2 is good. The connecting pipe between the superheater 4 and the vessel 12 is desirably larger than the pipe between the vessel 12 and the reboiler 3 and the reboiler 3 pipe. By making the pipe connected to the reboiler 3 smaller than the reboiler 3, flow path resistance is generated, and backflow is prevented. According to the present knowledge, as shown in the embodiment described later, a device (such as a check valve) for restricting the flow is not required, but there are advantages in using the device in some cases.

It is desirable that the cooling capacity has the same capacity as the heating. However, the selection of the refrigerant fluid is fluid depending on the required temperature and pressure.

In operation at a temperature of 400 ° C. and a pressure of 400 atm or more, especially in an aqueous solution, the equipment is provided with Hastelloy C-2.
It is desirable to use a corrosion resistant alloy such as 76, titanium, Inconel 625 and the like.

The operating device at 0.1 to 400 atmospheres is as follows.

The sample 25 is a container 12 having a high-pressure sample container.
And load inside. The liquid, the liquid mixture, the supercritical fluid, and the supercritical mixture are led from the filling port 21. In some cases, a solid such as dry ice can be directly introduced into the reboiler 3 and the superheater 4 as a solvent.

The driver selects an appropriate temperature and pressure program, and the operation proceeds by giving arbitrary software to the computer 23. Heating is controlled by the voltage applied to the reboiler 3 and the superheater 4. When the reboiler 3 and the superheater 4 become hot, the density of the solvent in the reboiler 3 and the superheater 4 decreases, and the fluid rises in the pipe due to the correlation between pressure, volume and temperature. This pressure
Since the volume-temperature correlation differs depending on the type of solvent or mixed solvent, the required fluid flow rate is determined by:
As is well known, it is derived from flow and heat transfer phenomena and thermodynamic quantities. That is, it depends on the heat transfer, the correlation of physical performance, and the equation of state.

In order to increase the circulation flow rate of the fluid, a cooler 15 and a supercooler 17 are used. However, when the heat loss is sufficient under external conditions, the operation can be performed without using. The phase state of a fluid changes between a liquid, a vapor-liquid (two-phase) mixture, a supercritical fluid, ie a dense gas.
If the liquid is near the boiling point or if the gas-liquid mixture is particularly close to the critical point, the pumping effect in the reboiler 3 will be very strong, increasing the contact between the sample and the solvent and assisting the mixing, and It is possible to overcome the problem of the invention of the present invention. The solvent passes through the sample to extract the target component, flows through the sample circulation circuit, returns to the reboiler 3, and after a certain period of time, the desired extract is concentrated in the solvent phase, and in some cases, crystallizes. During this extraction, the concentration of the sample reaches a concentration sufficient to perform various analyses. The multi-way valve 24 is used for this sampling. In the multi-way valve 24, 24a and 24b are an inlet and an outlet of a solvent, 24c and 24d are an inlet and an outlet of a concentrated sample,
Reference numerals 24e and 24f denote a mobile phase or a carrier gas inlet and outlet.

The length of the retention tube 26 is set to a length capable of holding the amount of the concentrated sample, and the volume is 1 μL to 10 mL. In the case of a large volume, a tube coil which is usually used is used. In addition, the extract is automatically controlled and rotated by a computer, and the extract can be periodically removed as needed. The rotation situation is shown in FIG. The sample is sent to the concentrated sampling port (on-line) as it rotates and changes as shown in figure b. The concentrated sample is sent to a usual analyzer and analyzed. It is preferable to maintain the solvent density of the high pressure circuit (line 2) by filling the sample circuit after analysis with the solvent used in the high pressure circuit as shown in FIG.

The advantage of this device is that the state of concentration accompanying extraction or reaction can be monitored over time without affecting the sample. Further, it is possible to use an adsorbent for concentrating the extract or to add a mild heating facility during the extraction or reaction in the retention pipe 26. The retention pipe 26 can be installed at any position in the circulation circuit. For maximum enrichment, it is desirable to place it in the lower part of the circuit as shown in FIG. From this knowledge, the flow rate of the extraction or reaction solvent is uniform and continuous through the vessel 12.

FIG. 3 shows the container 12 in detail.

This contains a sample 25, and is constituted by a high pressure pipe 27 of a cone-end type for fitting (the angle is generally 50 ° to 80 ° and generally 60 °). The gland nut 28 tightens the tubing ring 29 and can be safely and completely sealed within the pressure range used in the present invention.

FIG. 4 shows the details of the reboiler 3. The reboiler 3 has the same design as the container 12. In the present invention,
Fill 30 is used in reboiler 3 and superheater 4 to promote heat exchange and phase mixing. These are selected from the group consisting of Lahishling, Berel saddle, Interlock saddle, Terra Red, Palling and other fillers known as fillers. The structure and choice of the filler used are also important factors of the present invention. The material of the filler 30 is desirably ceramic, stainless steel, electropolished steel, or a similar material.

FIG. 5 shows an embodiment at an extremely high pressure (0.1 to 4,000 atm).

All parts used are of high temperature and high pressure specification,
Sampling is accomplished by installing a pair of three-way valves 31, 32 on line 2 or other suitable high-temperature, high-pressure sampling circuit.

The operation and the automatic circulation of the solvent were carried out in the reboiler 3,
The superheater 4 is controlled by the computer 23, and the cooler 15 and the supercooler 17 are operated as described in the high-pressure operation (FIG. 2). However, in the case of an ultra-high pressure, a slight change in operation is required. The cooler 15 and the supercooler 17 are used to increase the density difference between the fluid introduced into the reboiler 3 and the superheater 4. This can increase the particularly vigorous circulation performance at 4,000 atmospheres of ultra-high pressure.

In the mechanism shown in FIG. 5, sampling is performed as follows. First, the valves 31a and 32a are closed, and the automatic circulation occurs as described above.
2b is closed, and the sample is stored in the line 2. Next, the solvent to be used for analysis is introduced from the introduction tube 32c to the sample circuit, or introduced into the analysis instrument from the introduction tube 31c by opening the valves 31a and 32a. In order to maintain the density of the system, the sample circuit (line 2) is filled with fresh solvent or another substance, the solvent is continuously introduced from the inlet tube 32c and the valve 31
Close a and 32a. By opening the valves 31b, 32b, the density of the system is maintained, and by repeating the same process, a large amount of the desired sample can be taken, and the change with time of the extraction or reaction can be known.

FIG. 6 shows the procedure for carrying out the extraction and reaction at ultra-high pressure (0.1 to 10,000 atm). All parts used are ultra-high pressure and high temperature specifications. Sampling connects a pair of two-way valves 33, 34 to the sample circuit 35 or to a suitable high-temperature, high-pressure sample removal circuit. The operation and the automatic circulation of the solvent are performed by controlling the reboiler 3 and the superheater 4 with the computer 23, and the cooler 15 and the supercooler 17 are performed as described in the high-pressure operation circuit (FIG. 2). However, in the case of ultra-high pressure, only a two-way valve can be used, and since the density of the sample is high, there is a restriction and the degree of freedom is small. The cooler 15 or the supercooler 17 is for increasing the density difference between the fluids introduced into the reboiler 3 and the superheater 4, and for ensuring that heat-driven solvent circulation occurs even at an ultrahigh pressure. This additional measure can significantly increase performance at ultra-high pressures of 10,000 atmospheres.

In the mechanism shown in FIG. 6, sampling is performed as follows.

First, the automatic circulation step and the extraction or reaction are started as described above under the high pressure and ultra high pressure. In this case, valves 33 and 34
Is closed, and the sample circuit 35 is removed by several methods. The valve 34 is then opened, increasing the capacity of the system and reducing the pressure. After closing the valve 34, the valve 33 is opened and the sample is directed to a suitable analytical instrument by depressurization through the tube 36.

The system-attached equipment will be described in detail with reference to FIG.

As shown in FIG. 7A, the inlet / outlet 37, 38 of the cooler A with the hinge 36 may be installed at any position in the mechanism depending on the purpose of use. As shown in Fig. b, the microwave, ultrasonic or vibrator B with hinge 39 may be installed at any position of the mechanism depending on the purpose of use. As shown in Fig. c, the hinge-added heater C may be used at any position depending on the purpose of use.

FIG. 8 shows the mechanism of crystallization at ultra-high pressure (10,000 atmospheres). In this case the automatic circulation is started as described above and the additional cooler 41 is connected to the filtered collector 4
It faces 2 Crystallization can be performed at high pressure (400 atm) or ultra high pressure (4,000 atm).

FIG. 9 shows that the heterogeneous catalysis is performed at an ultra-high pressure (10,000
Pressure mechanism). Automatic solvent circulation occurs as described above, with an additional cooler 41 facing the catalytic reactor 43 containing the appropriate supported catalyst. A cooler 44 following the reactor 43 is used to terminate the reaction or limit the reaction rate. If it is necessary to remove the reaction product immediately, an adsorbent is installed immediately after the reactor 43.

FIG. 10 shows a mechanism for injecting additives and the like into the high-pressure vessel for solvent extraction or reaction after the automatic circulation of the solvent has reached a steady state. The valve position is extremely high pressure (4,
In the case of 000 atm), it is placed above and below as shown in the figure. The additive is put into the additive holder 49 by closing the valves 45, 46 and opening the valves 47, 48. At some time, the additive is introduced into the system and begins the extraction or reaction, at which time the valve 4
In the system of the present invention, which closes 7, 48 and opens valves 45, 46, the temperature is measured at various points, allowing control or tracking of the reaction or extraction when heat transfer is involved. Alternatively, the composition can be tracked over time by introducing one or more sampling valves. Or U
V, irradiation, infrared, Raman, EXAFS, turbidity or suitable optical analysis techniques can also be used.

In the above-mentioned apparatus, an extremely wide range of mixed solvents of organic, inorganic, and mixed solvents can be used. For example, carbon dioxide, carbon dioxide + additive,
There are water, water + additives, acidic or basic solvents, hydrocarbon mixtures, hydrocarbon + additives, additives and mixtures thereof.

As additives, alkanes, alkenes, cyclic or bridged hydrocarbons, aromatic, heterocyclic systems, cyclic, thio, imide, sulfone, ketoamino,
Acids, alkanoic acids, alkenoic acids, alkane diionic acids, acid halides, amines, alcohols, esters, acids, ethers, aldehydes, ketones, phenols, aromatics, amines, sulfides, Sulfide,
Sulfoxide, sulfone, surfactant, chelating agent, liganto, fluorine compound, acetylate ether and the like.

Next, various processing examples using the system of the present invention will be introduced.

Extraction Example 1 Paper impregnated with polychlorinated biphenyl (PCB) is put into an extraction column shown in FIG. As an extraction solvent,
Select carbon dioxide. The capacity of the system is usually 50cc. 30 cc of saturated liquid carbon dioxide is introduced into the system at 20 ° C. Reboiler 3 heating 500-1500W, super heater 4
Is heated at 500-1500 W, cooler 15 and supercooler 1
Rapid automatic circulation without cooling of 7 occurs within 3 minutes after heating. The first rapid two-phase flow is observed through a high-pressure window attached to the circuit (line 2). The pressure is
It gradually increases from 50 atm to 100 atm, after which the automatic circulation decreases but clearly continues. The time setting for PCB extraction is determined by periodic sampling by the multi-way valve 24. By performing the cooling with the cooler 15 and the supercooler 17, when the pressure gradually becomes 150 atm and the average temperature reaches the critical region at 60 ° C., the automatic circulation can be increased. In this example, full saturation of the solvent is achieved within 10-20 minutes.

Extraction Example 2 A soil containing petroleum hydrocarbons (PHC) is put into an extraction column of the apparatus shown in FIG. Select carbon dioxide + acetone (additive) as the extraction solvent. Generally 50 cc depending on the capacity of the system, and 2 cc of acetone and 35 cc of saturated liquid carbon dioxide are introduced into the system at 20 ° C. Reboiler 3
Is heated to 500 to 1500 W, and the superheater 4 is heated to 500 to 1500 W. Rapid automatic circulation occurs within 3 minutes after heating without cooling of the cooler 15 and the supercooler 17. The first rapid two-phase flow is observed from the high-pressure window installed in the circulation circuit. The pressure gradually increases from 50 atm to 150 atm, after which the automatic circulation decreases but clearly continues. The PHC extraction time is determined by periodic sampling by the multi-way valve 24. By performing cooling with the cooler 15 and the supercooler 17, when the pressure gradually reaches a critical region at 150 atm and an average temperature of 60 ° C., the automatic circulation can be increased. In this example, sufficient saturation of the solvent is achieved within 15-30 minutes.

Extraction Reaction Pacific coal is crushed into particles having an average diameter of 100 μm. About 10
g sample is placed in a ceramic container of an extraction column of high temperature and high pressure specification of the apparatus as shown in FIG. Normal capacity is
It is 40cc. About 20 cc of a mixture of 80/20 (W / W) water and toluene is charged to the reactor (line 2). When the reboiler 3 and the superheater 4 are heated at 1000 to 1500 W, rapid automatic circulation occurs within 5 minutes. The extraction temperature pressure increases according to the boiling point or the curve of the mixture. When the system enters the near supercritical or supercritical state, the reaction and the extraction occur in parallel, and the extracted sample is taken out from an appropriate sample valve. Liquefied coal is produced within 15 minutes.

Crystallization Approximately 25 cc of the water-soluble metal nitrogen compound is placed in the apparatus of FIG.
Normal system capacity is 30cc reboiler 3, super heater 4
Heat at 1000-1500W, cooler 15, additional cooler 4
1. When cooled by the supercooler 17, the pressure rises to several thousand atmospheres, and fine crystals of 10 to 20 nm precipitate due to the low solubility of the oxide in supercritical water. The crystallization process continues by removing a small sample from the sample circuit 35.

Heterogeneous Reaction Mixing a solvent near the critical point in a batch reactor is difficult because of its high pressure. This means that it is difficult to carry out a large amount of reactions. FIG.
Approximately 1 g of the NiMo catalyst is put into the catalyst reactor 43 shown in FIG. A compound containing sulfur, dibenzothiophenone, is introduced into the reactor. Pressurize the system with carbon dioxide to reduce the overall density to 0.
Adjust to 6. 100 heaters for reboiler 3 and super heater 4
Automatic circulation starts by heating at 0-1500W.
The reaction time can be completed in 10 minutes in this method, even if it takes several hours in a method in which ordinary catalyst / reactant contact and mixing are poor.

Dyeing The fiber is put into the extraction part 12a of the sample filling container 12 shown in FIG. The dye is put into the additive holder 49. A mixture of carbon dioxide + ethanol 90/10 (w / w) is heated to a reboiler 3 and a superheater 4 to 1000-1500 W, and a cooler 1
5. When the supercooler 17 is activated, the system is stable,
Start regular circulation. Valves 45 and 46 are opened and valve 47 is opened.
And 48 close. The dye gradually comes into fiber contact, and the dyeing reaction occurs almost completely in a single contact. The flow occurs smoothly even in the supercritical region, and a uniform and good result can be obtained by using the saturated state.

[0063]

Since the present invention is configured as described above, the following effects can be obtained.

In the system, extraction sufficient to be able to be connected to an analyzer for ultra-trace components is possible, and furthermore, concentration and crystallization can be performed, and the input fluid is repeatedly brought into contact with the object to be treated. Is not limited to ultra-trace component extraction, but enables various extraction reactions, crystallization, heterogeneous reactions, and dyeing, which have been difficult so far, and greatly contributes to this field.

As a result, for example, a geological sample (soil, rock, coal), a biochemical sample (animal tissue, bone), an agricultural sample (beans, cereals, stems), or a chemical industry sample (tar, Residue, sludge, ceramics,
It can be applied to extraction, concentration, and analysis of trace components without using the inefficient Soxhlet method.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a basic configuration of a system of the present invention.

FIGS. 2 (a) and 2 (b) are an explanatory view of an apparatus for 0.1 to 400 atm of the system of the present invention and an explanatory view of operation of a main part.

FIG. 3 is a detailed explanatory view of a sample filling container in the system of the present invention.

FIG. 4 is a detailed explanatory view of a reboiler of the system of the present invention.

FIG. 5 is an explanatory view of a device for 0.1 to 4,000 atmospheres of the system of the present invention.

FIG. 6 is an explanatory view of a device for 0.1 to 10,000 atm of the system of the present invention.

FIGS. 7A, 7B and 7C are explanatory diagrams of a cooler, a vibrator, and a heater of various external contact devices in the system of the present invention.

FIG. 8 is an explanatory view of an apparatus for crystallization of the system of the present invention.

FIG. 9 is an explanatory view of an apparatus for heterogeneous catalytic reaction of the system of the present invention.

FIG. 10 is an explanatory view of an apparatus for injecting additives in the system of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cabinet 2 Supercritical fluid circulation high pressure pipe 2a Vertical path 2b Vertical path 3 Reboiler 3a Heating body 4 Superheater 4a Heating body 5 Temperature controller 6 Temperature controller 7 Thermocouple 8 Thermocouple 9 Electric sensor 10 Measuring instrument 11 Burst Plate 12 Sample filling container 13 Thermocouple 14 Cooling unit 15 Cooler 16 Cooling unit 17 Supercooler 18 Valve 19 Valve 20 Analysis tube 21 Solvent filling port 22 Thermocouple 23 Computer 24 Multi-way valve 24a Solvent inlet 24b Solvent outlet 24c Concentration Sample inlet 24d Concentrated sample outlet 24e Mobile phase or carrier gas inlet 24f Mobile phase or carrier gas outlet 25 Sample 26 Retention pipe 27 High pressure pipe 28 Ground nut 29 Tubing ring 30 Filling 31 Three-way valve 31a Valve 31b Valve 31c Introduction Tube 32 Three-way valve 32a valve 32b valve 32c introduction pipe 33 two-way valve 34 two-way valve 35 sample circuit 36 hinge 37 inlet 38 outlet 39 hinge 40 hinge 41 cooler 42 collector 43 reactor 44 cooler 45 valve 46 valve 47 valve 48 valve 49 Additive holder

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masayuki Kanno 1-19-23 Nishi-Odori, Hanamaki-shi, Iwate F-term (reference) 4D056 AB01 AB17 AC24 BA05 BA11 BA16 CA37 CA40

Claims (8)

[Claims] 1. A supercritical fluid to be filled is heated at a lower portion of one of the vertical supercritical fluid circulation pipes through a filling port provided at an appropriate portion of the pipe to lower the density. A reboiler consisting of an external contact device and a superheater consisting of an external contact device for increasing the density gradient by further heating are arranged above the reboiler, and a sample filling container consisting of a mesh body is arranged in the middle of the other longitudinal path. The solvent is automatically circulated as a driving force using the density difference generated by the heating of the reboiler and the superheater and the cooling at room temperature in the other longitudinal path, and the subject to be analyzed is obtained by repeated contact of the same solvent with the sample by the circulation. An extraction and washing system using a supercritical fluid that condenses at room temperature as a solvent, wherein the extraction is performed and sampling is performed from an appropriate portion of the above-mentioned conduit. 2. A supercritical fluid filled in a lower portion of one of the vertical supercritical fluid circulation pipes is heated by a filling port provided at an appropriate portion of the pipe to reduce the density. A superheater consisting of an external contact device for increasing the density gradient by further heating is arranged on the reboiler consisting of an external contact device and a higher order, and a sample filling container consisting of a mesh body and a higher order above the other longitudinal path. A cooler comprising an external contact device for cooling and increasing the density of the fluid is provided, and a supercooler comprising an external contact device is provided at the lower part of the pipeline to promote the higher density of the lower portion of the pipeline, The solvent is automatically circulated using the difference in density between the heating of the reboiler and the superheater and the cooler in the other longitudinal path and the supercooler at the bottom as a driving force, and repeated contact of the same solvent with the sample by the circulation. Analysis at An extraction and washing system using a supercritical fluid as a solvent, wherein said extraction and washing are performed by sampling from an appropriate portion of said conduit. 3. A sampling system for a pressure of 0.1 to 400 atm, wherein sampling is performed by a multi-way valve disposed at the bottom of the supercritical fluid circulation line.
An extraction and washing system using the supercritical fluid as a solvent. 4. The method according to claim 1, wherein the sampling is performed between a pair of three-way valves disposed at the bottom of the supercritical fluid circulation line.
An extraction and washing system using a supercritical fluid as a solvent according to claim 2 for atmospheric pressure. 5. The supercritical fluid according to claim 2, wherein the sampling is carried out between a pair of two-way valves provided in a sample circuit branching off at the bottom of the supercritical fluid circulation pipe for 0.1 to 10,000 atmospheres. An extraction and washing system using a fluid as a solvent. 6. An extraction system using a supercritical fluid as a solvent according to claim 5, wherein a collector is provided at the bottom of the extraction column, and an additional cooler comprising an external contact device is provided opposite to the collector. An extraction and washing system using a supercritical fluid as a solvent for crystallization under high pressure. 7. The extraction system using a supercritical fluid as a solvent according to claim 5, wherein a catalyst reactor is formed in the extraction column and an additional cooler comprising an external contact device is provided in the catalyst reactor. And an extraction and washing system using a supercritical fluid as a solvent for a heterogeneous catalytic reaction under ultra-high pressure, in which a cooler for terminating or restricting the reaction comprising an external contact device is disposed below the catalytic reactor. 8. A supercritical fluid filled in a lower portion of one of the vertical supercritical fluid circulation pipes is heated by a filling port provided at an appropriate portion of the pipe to lower the density of the supercritical fluid circulation pipe. A reboiler consisting of an external contact device and a superheater consisting of an external contact device for increasing the density gradient by further heating are arranged above the reboiler, and a sample filling container or a reactor consisting of a mesh body is arranged on the other vertical path. A valve mechanism having a cooler composed of an external contact device that cools a fluid and increasing the density thereof, and a cooler composed of an external contact device disposed below the cooler, and having an additive retainer above the pipeline. The solvent is automatically circulated by using the difference in density between the heating of the reboiler and the superheater and the cooler in the other longitudinal path as a driving force, and the automatic circulation of the solvent reaches a steady state when the automatic circulation of the solvent reaches a steady state. Additive injection enabled An extraction and washing system using a supercritical fluid as a solvent.