JP2002350411A - Liquid chromatograph equipped with solvent recycle device and recovery method of used solvent using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid chromatograph equipped with a solvent recycle device and its recovery method for recovering a regenerated solvent including no moisture from waste liquid generated from G. P. C or the like. SOLUTION: This method has this liquid chromatograph 11 in a circulatory system, and this solvent recycle device 31. The method has, between a detector 19 and a first solvent storage vessel 12 and/or a second solvent storage vessel 13, at least a moisture removing column 51 filled with zeolite granule (molecular sieve) 53 containing an indicator in order to remove moisture from a moving phase introduced as the waste liquid W, a pressure-tight distillation part 32 formed so as to freely control heating to distillate the moving phase after moisture removal in inert gas, and a cooling part 45 formed so as to introduce the vapor in the pressure-tight distillation part 32 together with the inert gas, cool, liquefy it, and to freely reflux into the solvent storage vessels. Hereby, the regenerated solvent S2 containing no moisture is recovered from the waste liquid W. The liquid chromatograph and the solvent recycle device can be arranged in a non-circulatory system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid chromatograph provided with a solvent recycling apparatus for recovering and recycling a used solvent which has become waste liquid through a detector such as a differential refractive index detector as a regenerated solvent. , Especially a liquid chromatograph equipped with a solvent recycling device suitable for reusing waste liquid in gel permeation chromatography (hereinafter abbreviated as "GPC") and recovery of used solvent using the same About the method.

[0002]

2. Description of the Related Art FIG. 4 schematically illustrates a flow channel system formed by a conventional liquid chromatograph 1, in which a mobile phase is formed in a solvent storage tank 2 located at the uppermost stream. the solvent 3 has been stored for one end connected to filter F that is submerged in the solvent 3, the other end is formed with a delivery tube L ₁ taken to the outside .

[0003] The other end of the delivery tube L ₁ is connected to the side of the pump 4, so that the solvent 3 in the solvent storage tank 2 can be pumped to the downstream side by passing through the pump 4 It has become.

On the other hand, on the downstream side of the pump 4, a separation column 6 is disposed so as to be able to control the column temperature, and a connecting tube L ₂ that forms a flow path between the pump 4 and the separation column 6. Is provided with a sample injector 5 for injecting the sample into the solvent, and the like, so that the mobile phase after the sample injection can flow down to the separation column 6.

[0005] Downstream of the separation column 6, a detector 7 which is connected via a tube L _3, it is detected by the detector 7, and recorder for recording the result of the analysis (Fig. Shimese not) is installed, the mobile phase comprising a solvent which has become unnecessary after the analysis is stored as waste liquid 9 into the waste tank 8 is positioned furthest downstream of the channel system via the tube L _4, the All had been disposed of.

[0006]

However, according to the conventional liquid chromatograph 1, after a large amount of expensive organic solvents and reagents are used, the entire amount is discarded as a waste liquid 9, resulting in an increase in running costs. Not only that, there is a need for waste liquid treatment to take measures to prevent environmental pollution, and there is a problem that workers may be exposed to organic solvents.

[0007] In particular, G.I. P. C
Is widely used mainly in the polymer chemical industry,
The chemical solvents used (eg, chloroform, tetrahydrofuran, etc.) also tend to cause environmental pollution problems due to the strong solubility of the substance. Therefore, there has been a strong demand for recovery and reuse after use. However, the development of a truly effective recovery system has been delayed, and there has been a problem that illegal dumping may cause soil and air pollution.

Further, when water is contained in the solvent, hydrochloric acid is generated to damage the entire apparatus including the separation column, so that the separation column and the like do not last long.

In view of the above-mentioned problems in the prior art, the present invention provides a liquid chromatograph having a solvent recycle device that allows a used solvent that has been a waste liquid through a detector to be recovered as a regenerated solvent and reused. In particular, G. P. It is an object of the present invention to provide a liquid chromatograph provided with a solvent recycling device suitable for reusing a waste liquid in C and a method for recovering a used solvent using the same.

[0010]

Means for Solving the Problems The present invention has been made to achieve the above object, and among them, the first invention is:
It is composed of a liquid chromatograph and a solvent recycling device that are combined to form a circulation system as a whole, and the liquid chromatograph is configured to store a solvent in a solvent storage tank, and to pump the solvent from the solvent storage tank downstream. With a pump placed
A sample injector for injecting a sample into a solvent pumped through the pump, a separation column into which a mobile phase flows after the sample is injected into the solvent, and detection of sample components in the mobile phase passing through the separation column A solvent recycling device disposed between the detector and the solvent storage tank, the solvent recycling device being disposed between the detector and the solvent storage tank. A water removal column filled with zeolite granules (molecular sieve) containing an indicator for removing water from the phase, and a mobile phase as a waste liquid from which water has been removed through the water removal column are placed in an inert gas. A pressure-resisting distillation unit formed freely to control heating at an appropriate temperature determined by the relationship with the boiling point of the solvent that is a component to be distilled, and a vapor generated in the pressure-resisting distillation unit is introduced together with an inert gas. Retirement, liquefying, is characterized in configuration to comprise at least a cooling unit which is freely form a reflux to the solvent storage tank as a reproduction solvent.

[0011] In the first aspect, the solvent storage tank may include:
It is composed of a solvent first storage tank and a solvent second storage tank in which the flow path can be freely switched via a flow path switching valve, and these first solvent storage tank and second solvent storage tank are deodorizing containers containing powdered activated carbon. It is preferable that the air and the air check container containing the water liquid are sequentially connected to each other through a connecting pipe so as to be freely ventilated.

Further, the second invention comprises a liquid chromatograph and a solvent recycling device which are combined to form a non-circulating system as a whole, and the liquid chromatograph comprises a solvent storage tank for storing a solvent, A pump arranged to pump the solvent downstream from the solvent storage tank, a sample injector for injecting a sample into the solvent pumped through the pump, and a separation into which the mobile phase after injecting the sample into the solvent flows A column, a detector for detecting a sample component in the mobile phase passed through the separation column,
A recorder for recording the detection result by the detector, and at least a preparative collector into which waste liquid from the detector is introduced via a flow path switching valve and one of the flow paths; A solvent recycling device disposed between the waste liquid container into which the waste liquid from the detector is introduced via the other controlled flow path and the solvent storage tank is forcibly introduced as waste liquid from the waste liquid container. A water removal column filled with zeolite granules (molecular sieve) containing an indicator for removing water from the mobile phase, and a mobile phase as a waste liquid from which water has been removed through the water removal column are inert gas. A pressure-resistant distillation section formed freely to control heating at an appropriate temperature determined by a relationship with a boiling point of a solvent as a component to be distilled in the inside, and a vapor generated in the pressure-resistant distillation section is inert gas. And a cooling unit formed so as to be cooled and liquefied and circulated into the solvent storage tank as a regenerating solvent.

[0013] In the second aspect, the solvent storage tank may include:
It is preferable to sequentially connect the deodorizing container containing the powdered activated carbon and the air check container containing the water solution in a freely permeable manner through a connecting pipe.

Further, in the first and second aspects of the present invention, the pressure-resistant distillation section in the solvent recovery device may include:
A cylindrical pressure-resistant container inclined so that the waste liquid introduced through the detector flows down, a temperature sensor installed in the internal space of the pressure-resistant container, and ON / OFF in relation to the temperature detected by the temperature sensor. A cooling unit configured to at least include a heater that is turned off to freely heat a peripheral portion including a liquid reservoir of the pressure-resistant container, and an inert gas supply unit that can freely control the supply of an inert gas into the pressure-resistant container; Is a constant-temperature block capable of maintaining a predetermined cooling temperature, and is connected to a flow path derived from the pressure-resistant container and is introduced into the constant-temperature block, and at least an upstream side thereof is located at a lower side, and a downstream side is provided. It is desirable to form at least a conduit which is spirally arranged at the upper side and led out into the solvent storage tank.

On the other hand, the third invention uses a liquid chromatograph provided with the solvent recycling device according to any one of the first and second inventions described above to remove water from waste liquid after use. There is a structural feature in recovering the removed regenerated solvent.

[0016]

FIG. 1 is a schematic explanatory view showing an example of a first invention suitable for analysis among the present invention. P. The liquid chromatograph 11 applied to C and the like includes a first solvent storage tank 12 and a second solvent storage tank 13 in which a solvent S ₁ made of tetrahydrofuran (THF) is separately stored. a pump 15 which is arranged to pump the solvent S ₁ flowing through the valve 14 switching filter F and the flow path from the solvent second reservoir 13. to the downstream, the solvent S ₁ pumped through the pump 15
A sample injector 16 for injecting a sample therein, a separation column 17 into which a mobile phase after injecting the sample into the solvent S ₁ , and a differential refractive index for detecting a sample component in the mobile phase passing through the separation column 17 A detector 18 such as a detector, and the detector 1
And a recorder 19 for recording the result of detection by the controller 8. In addition, reference numeral 20 in the drawing indicates a conduit from the first solvent storage tank 12 and the second solvent storage tank 13 to the detector 18. When the solvent S ₁ is, for example, chloroform or the like, one of the solvent first storage tank 12 and the solvent second storage tank 13 is used as a solvent storage tank, and the solvent S ₁ is transferred downstream without passing through the flow path switching valve 14. Can be directly connected to the pump 15 for pressure feeding to the pump 15.

The solvent first storage tank 12 and the solvent second storage tank 1
3 is connected to a conduit 47.
An air check vessel sequentially, not shown water solution containing such a deodorization vessel 21 of powdered activated carbon C containing deodorizing inert gas introduced at the same time to recirculate the regeneration solvent S ₂ after liquefaction distilled water from These are mutually connected via a connecting pipe 22 so as to be able to ventilate.

In addition, the detector 18 and the flow path switching valve 1
Between the 4, is refluxed to the solvent first storage tank 12 or the solvent in the second storage tank 13 incorporates a reproduction solvent S ₂ water was removed from the waste liquid W in the mobile phase which has finished the process of detecting a sample component Therefore, the solvent recycling apparatus 3 mainly composed of the water removal column 51, the pressure distillation unit 32, and the cooling unit 45
1, the solvent recycle device 31 and the liquid chromatograph 11 form a circulating system that is brought online as a whole. When one of the solvent first storage tank 12 and the solvent second storage tank 13 is used as a solvent storage tank, the regenerated solvent S ₂ is refluxed to the solvent storage tank without passing through the flow path switching valve 14 so as to be online. It is also possible to form a simplified circulation system.

In this case, as shown in FIG. 2, the water removal column 51 disposed between the conduits 43, 43 has a cylindrical shape made of hard glass with high pressure resistance. Body 52, bead-shaped zeolite granules (molecular sieve) 53 having a particle size of, for example, about 2 mm containing an indicator filled in the cylindrical body 52, and an inflow port 52 a side of the cylindrical body 52 as appropriate. A filter 56 arranged together with the packing 55 via a sealing plug 54 having a structure, and a filter 59 similarly arranged together with the packing 58 via the sealing plug 57 on the outlet 52b side of the tubular body 52 are provided. The whole is formed. Note that reference numeral 60 in FIG.
Indicates an interposing ring for sealing. In addition, zeolite granules (molecular sieve) 53 may be 1 to 3 m if desired.
Those having an appropriate particle size such as m can be used, and those having different particle sizes can be mixed.

In this case, it is preferable to use phenolphthalene as the indicator, and by using this, if the zeolite granules (molecular sieves) 53 contain moisture, the alkali metal will dissolve out of the zeolite granules 53 and exhibit alkalinity. Therefore, the appearance of phenolphthalene changing from orange to colorless and transparent can be visually confirmed. Therefore, by confirming the color change of phenolphthalene, it is possible to immediately know how much water the zeolite granules 53 capture.

On the other hand, the pressure-resistant distillation section 32 of the solvent recycling apparatus 31 is provided with a solvent S _{1 as} a component to distill the waste liquid W flowing through the detector 18 at a flow rate of about 1 ml / min in an inert gas. The heating control at an appropriate temperature determined by the relationship with the boiling point, for example, at a temperature about 15 to 25 ° C. higher than the boiling point of the solvent S ₁ is freely formed. The cooling unit 45, the flow path switching the first storage tank 12 or solvent solvent through the valve 14 the steam generated by the cooling and liquefaction is introduced together with an inert gas as regeneration solvents S ₂ at the breakdown voltage the distillation unit 32 It is formed so as to freely return to the two storage tanks 13.

This will be described in more detail with reference to FIG. 1. The pressure-resistant distillation section 32 is provided with, for example, a horizontal line so that the waste liquid W introduced from the detector 18 through the conduit 43 flows down smoothly. And a cylindrical pressure-resistant container 33 which is inclined at an appropriate angle in the range of 30 to 90 degrees, preferably 45 to 80 degrees, and an upper stopper for sealing the upper opening of the pressure-resistant container 33 And a temperature sensor 35 introduced into the internal space 33a through the inner space 34, and a detection temperature of the temperature sensor 35 by, for example, winding a nichrome wire around an outer peripheral surface 33c of the pressure-resistant container 33 including a liquid reservoir 33b. The heater 37 is provided so that the heating control can be freely performed through the temperature controller 36 whose ON / OFF control can be freely performed in the relation described above, and the supply control of the inert gas into the pressure-resistant container 33 is freely provided. Inert gas supply 38, and at least a suction / discharge tool 42 provided for forcibly sucking and discharging to the outside as soon as the residual amount including the analyzed residual sample stored in the liquid storage portion 33b reaches a predetermined amount. Is formed.

In this case, a pressure-resistant container 33 designed to withstand a pressure of about 50 atm is made of a pressure-resistant glass material having a heat resistance of about 200 degrees Celsius and an organic solvent resistance, a stainless steel material and a fluororesin. A member formed of a material or the like can be preferably used. In addition, the pressure vessel 33
For example, a material having an airtight structure that is resistant to high pressure and has high airtightness, for example, employed in a preparative column can be preferably used.

As the temperature sensor 35, a temperature sensor formed by incorporating a thermocouple in an airtight manner in a cover material having a high corrosion resistance such as a stainless steel cover can be suitably used.
The heater 37 can also be formed by an electric heating structure including a ceramic heater, an infrared heater, or the like provided on a peripheral portion including the liquid reservoir 33b of the pressure-resistant container 33, for example, on the outer peripheral surface 33c. Further, it is desirable to control the heating temperature of the heater 37 so that it can be set to a temperature that is about 10 to 25 ° C. higher than the boiling point in relation to the boiling point determined according to the type of the wastewater W flowing in.

The inert gas supply section 38 includes a gas cylinder 39 filled with an inert gas such as a nitrogen gas or a helium gas, and a gas introduced from the gas cylinder 39 into the pressure-resistant container 33 through the upper stopper 34. Pipe 40 and said gas pipe 40
And a valve 41 that is interposed in the flow path and controls the flow rate of the supply gas.

The cooling unit 45 is at room temperature (25 degrees Celsius) or less,
For example, a constant temperature block 46 formed so as to be able to maintain a cooling temperature of about 5 to 15 degrees Celsius, and a flow path switching valve 14 derived from the pressure-resistant container 33 and passing through the constant temperature block 46.
And at least a conduit 47 leading to the end.

The constant-temperature block 46 is made of a metal material having an appropriate heat conductivity and an appropriate volume, such as copper, aluminum, stainless steel, brass, and solder. Instead of a liquid-cooled type, a cooling fin (not shown) is attached to the outer peripheral surface, and an air-cooled type that can be easily cooled to a predetermined cooling temperature by receiving the wind of a cooling fan (not shown) arranged in the vicinity. It is desirable to adopt.

The conduit 47 is provided with an inflow portion 48 for introducing steam from the pressure-resistant container 33 into the thermostatic block 46, an upstream side of the inflow portion 48 in the thermostatic block 46, and a downstream portion thereof. A heat exchange part 49 spirally arranged in an arrangement relation in which the side is positioned on the upper side;
Their entirety by communication passage consisting of the outflow section 50. for the regeneration solvent S ₂ that is liquefied and refluxed from the side into the channel switching valve 14 of is formed. In this case, conduit 4
7 is desirably formed of a stainless steel tube which exhibits excellent corrosion resistance to an organic solvent. The heat exchange part 49 of the conduit 47 has a spiral through-hole in the constant temperature block 46 based on the above-described arrangement, and connects the upstream side to the inflow part 48 and the downstream side to the outflow part 50. Alternatively, it can be formed.

On the other hand, FIG. 3 is a schematic explanatory view showing an example of a second invention suitable for fractionation in the present invention. P. The liquid chromatograph 111 applied to C or the like includes a solvent storage tank 112 in which an appropriate solvent S ₁ is stored.
And the solvent S from the solvent storage tank 112 via the filter F.
Pump 115 arranged to pump ₁ downstream, a sample injector 116 to inject a sample into the solvent S ₁ pumped through the pump 115, and movement after injecting the sample into the solvent S ₁ A separation column 117 into which a phase flows, a detector 118 such as a differential refractive index detector for detecting a sample component in the mobile phase passing through the separation column 117, and the detector 118
, And at least a fraction collector 126 into which waste liquid from the detector 119 is introduced via the flow path switching valve 125. In the drawing, reference numeral 120 denotes a conduit from the solvent storage tank 112 to the detector 118, and reference numeral 121 denotes a solvent storage tank 11
2 is a deodorizing container containing powdered activated carbon C which is communicated via line 122, and 123 is an air check container containing water L such as distilled water which is communicated with the deodorizing container 121 via line 124. Are respectively shown.

In addition, a water removal column 51 shown in FIG. 2 is interposed between the waste liquid container 127 and the other flow path 130, which is controlled to be switched via the detector 118 and the flow path switching valve 125. . The water removal column 51
Is the same as that in FIG. 1,
The description is omitted.

Further, the waste liquid container 127 and the solvent storage tank 112
And between the waste liquid container 12 and the
The waste liquid W as the mobile phase stored in the pump 7 is pumped.
Through 28 and the flow path 129 forcibly sucking, composed of in waste liquid W in order to reflux to a solvent storage tank 112 takes in the playback solvent S ₂ that does not contain moisture, the breakdown voltage distillation unit 132 and the cooling unit 145 A solvent recycling device 131 to be used is interposed, and the solvent recycling device 131 and the liquid chromatograph 111 form an off-line non-circulating system.

In the second embodiment, the pressure distillation unit 132 and the cooling unit 1 constituting the solvent recycling unit 131
45 has the same structure as the pressure-resistant distillation unit 32 and the cooling unit 45 shown in FIG. 1, and the detailed description thereof will be omitted by attaching the same reference numerals to the respective constituent members.

Next, the third invention (method of recovering used solvent) of the present invention will be described in relation to the operation of the first invention.

That is, G. P. By using the liquid chromatograph 11 applied to C and the like, the solvent first storage tank 12 and the solvent second storage tank 1
3, the solvent S ₁ is pumped downstream via the pump 15, and the sample is injected by the sample injector 16 into the solvent S _1.
The mobile phase after having been injected into it can flow into the separation column 17. The sample components in the mobile phase that have passed through the separation column 17 are detected by a detector 18 such as a differential refractive index detector, and the result of the detection can be recorded by a recorder 19.

The waste liquid W as a mobile phase which is led out from the detector 18 via the conduit 43 is introduced into the water removal column 51 interposed between the conduits 43.

At this time, since the zeolite granules (molecular sieves) 53 in the form of beads having a particle diameter of, for example, about 2 mm and containing phenolphthalene as an indicator are filled in the water removal column 51, and are introduced. The waste liquid W passes through with water removed. It should be noted that phenolphthalene as an indicator changes its color from orange to colorless and transparent as the zeolite granules (molecular sieves) 53 capture moisture, so it is necessary to determine how much moisture the zeolite granules 53 capture. The user can immediately know the necessity, and easily know whether or not the replacement of the water removal column 51 is necessary.

The waste liquid W from which the water has been removed is filled with an inert gas supplied with an inert gas supplied by an inert gas supply unit 38 so as to control the amount of supply, instead of air. By allowing the liquid to flow naturally into the disconnected pressure-resistant container 33, it is possible to smoothly flow the liquid into the liquid reservoir 33b.

In addition, the pressure vessel 33 designed to withstand a pressure of about 50 atm is set so that the temperature can be set to a temperature that is about 10 to 25 degrees Celsius higher than the boiling point of the used solvent in the waste liquid W. Since the controlled heater 37 is provided on the outer peripheral surface 33c, for example, the waste liquid W flowing down the inner surface and the solvent component contained in the waste liquid W flowing into the liquid reservoir 33b are brought to a boiling point as the temperature rises. As a result,
Almost all of it becomes steam and rapidly expands its volume, while safely increasing the pressure in the internal space 33a. In this case, the pressure vessel 33 communicates with the solvent first storage tank 12 or the solvent second storage tank 13 via the flow path switching valve 14 and the conduit 47, and the solvent first storage tank 12 and the solvent second storage tank 13 are connected to each other. Since it communicates with the deodorizing container 21 through the passage 22, as the internal pressure increases, the pressure-resistant container 33
→ Cooling unit 45 → Solvent first storage tank 12 or solvent second storage tank 13 → Deodorization vessel 21 → Communication flow path with positive pressure capable of releasing deodorized inert gas to the outside via an air check container (not shown) Will be done.

Thus, the vapor composed of the solvent component which does not contain the outside air component and the moisture is supplied to the internal space 33a of the pressure vessel 33.
As the internal pressure increases, the gas is fed from the inflow section 48 to the heat exchange section 49 together with the inert gas, and the heat exchange section 49 is positioned such that its upstream side is located lower in the constant temperature block 46 and downstream since the side is helically disposed under the relationship of allocation is positioned on the upper side, reproducing the solvent S ₂ next to be smoothly cooled and liquefied in the absence of air components on a moisture free during its passage, the outflow through the part 50 is recovered by refluxing into a solvent first storage tank 12 or the solvent in the second storage tank 13, leading to the re-used with a solvent S _1.

That is, since the liquid chromatograph 11 and the solvent recycling device 31 are formed as a circulating system in which the sample is injected into the solvent S ₁ , the mobile phase formed by injecting the sample into the solvent S ₁ passes through the detector 18 to the waste liquid W and becomes even, waste liquid W by going through the solvent recycling device 31, regeneration and water and the analyzed sample components are removed solvent S ₂ as the solvent first storage tank 12 or solvate second tank 13
It can be reused by refluxing and collecting inside
Addition can contribute to resource conservation, which is the needs of the times by reducing the consumption of expensive solvents S _1, will be able to also contribute effectively to reduction of running cost. Play solvent S _2, since it is possible to recirculate without incorporation of outside air component, it is also possible to improve the accuracy of analysis by reducing the occurrence of various troubles derived from the incorporation of outside air component.

Further, the solvent component contained in the waste liquid W is as follows:
Substantially the entire amount without being discarded can be recovered as the playback solvent S ₂ containing no water. Therefore, if it contains moisture during playback solvent, there was a risk of damage to the entire device 11 including a separation column 17 by generating hydrochloric acid, the regeneration solvent S ₂ according to the present invention water Is not included, so that the separation column 17 and the like can be made to last longer. In addition, it is also possible to effectively prevent environmental pollution, which is likely to be caused by used solvents, which are regarded as dangerous substances. Note that when the solvent S ₁ is a tetrahydrofuran (THF), it is necessary to prevent contamination oxidizing agent so easily generates peroxide (BHT) in advance, the playing solvent S ₂ Since the antioxidant (BHT) is not contained, the antioxidant (BHT) is additionally mixed in after being recovered to the solvent first storage tank 12 or the solvent second storage tank 13 via the flow path switching valve 14. .

On the other hand, the third invention (method of recovering used solvent) of the present invention will be described in relation to the operation of the second invention. P. By using the liquid chromatograph 111 applied to C or the like, the solvent S ₁ is pumped downstream from the solvent storage tank 112 via the pump 115, and after the sample is injected into the solvent S ₁ by the sample injector 116. Can flow into the separation column 117. The sample component in the mobile phase that has passed through the separation column 117 is detected by a detector 118 such as a differential refractive index detector, and the detection result can be recorded by a recorder 119.

In the liquid chromatograph 111, the waste liquid W can flow from the detector 119 to the collection collector 126 via the flow path switching valve 125 to separate the substance.

Further, the waste liquid W flowing out of the detector 119
Is water interposed between the flow path 130 and the waste liquid container 127.
Water is removed by passing through the column 51
In the waste liquid container 127 via the flow path switching valve 125
It can also be stored temporarily. In this case, waste container
The waste liquid W after the removal of water in 127 is passed through a pump 128.
And forcibly aspirated it, as shown in FIG.
Solvent recycling device configured in the same manner as the
And the solvent recycling device 131 is
As a result, moisture and analyzed sample components are removed.
Recycled solvent S _Two As reflux in the solvent storage tank 112
Expensive solvent S because it can be recovered and reused ₁ Consumption of
Can contribute to the resource savings demanded by the times.
In addition to effectively reducing running costs
Can be done. Also, the regeneration solvent S_Two Is the water
Reflux without mixing air and components
Can cause damage to the separation column 17 and the like due to residual water.
In addition to eliminating scratches, airborne components
To improve the analysis accuracy by reducing the occurrence of various troubles
Can be done.

In particular, G. G. as a molecular weight distribution measuring method widely used in the polymer chemical industry. P. By applying the present invention to C, for example, even chemical solvents such as chloroform and tetrahydrofuran, which are likely to cause environmental pollution problems, can be recovered and reused after use. It can also avoid contamination.

[0046]

As described above, according to the present invention, a mobile phase obtained by injecting a sample into a solvent can be analyzed with high accuracy by a detector, and also from the side of the detector. The waste liquid flowing down is heated in an inert gas in the pressure-resistant distillation section at a temperature higher than the boiling point of the used solvent, and almost all of the solvent components are converted into steam containing no moisture and outside air components. By introducing it to the cooling section together with the gas and cooling and liquefying it, it can be refluxed as a regenerating solvent, collected and reused, so that consumption of expensive solvents can be reduced and resources can be saved, and running costs can be reduced. Can also be effectively reduced. In addition, since the regenerated solvent can be refluxed without mixing moisture and outside air components, it is possible to eliminate damage to the separation column and the like caused by remaining moisture, and to prevent various types of impurities caused by mixing of air components. The occurrence of trouble can be reduced and the analysis accuracy can be improved.

In addition, since almost all of the solvent components contained in the waste liquid can be recovered as a regenerated solvent without being discarded, most of them are caused by a used solvent which is regarded as a dangerous substance. Pollution can be effectively prevented.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing an example of the first invention in the present invention.

FIG. 2 is a longitudinal sectional view showing a structural example of a water removal column used in the present invention.

FIG. 3 is a schematic explanatory view showing an example of the second invention in the present invention.

FIG. 4 is a schematic explanatory view showing a configuration example of a conventional liquid chromatograph.

[Explanation of symbols]

11,111 Liquid chromatograph 12 Solvent first storage tank 12a Upper space 13 Solvent second storage tank 13a Upper space 14 Channel switching valve 15,115 Pump 16,116 Sample injector 17,117 Separation column 18,118 Detector 19,119 Recorder 20 Pipe 21 Deodorizing container 22 Pipe 31 Solvent recycling device 32 Pressure-resistant distillation unit 33 Pressure-resistant container 33a Internal space 33b Liquid reservoir 33c Outer peripheral surface 34 Upper plug 35 Temperature sensor 36 Temperature controller 37 Heater 38 Inert gas supply unit 39 Gas cylinder 40 Gas pipe 41 Valve 42 Discharge tool 43 Conduit 45 Cooling unit 46 Constant temperature block 47 Conduit 48 Inflow unit 49 Heat exchange unit 50 Outflow unit 51 Water removal column 52 Tubular body 52a Inlet 52b Outflow 53 Zeolite granule (molecular sieve) 54 , 57 Sealing plug 55, 58 Packing 56, 59 Filter 60 Intermediate ring 112 Solvent storage tank 120 Line 121 Deodorizing container 122 Line 123 Air check container 124 Line 125 Flow path switching valve 126 Preparative collector 127 Waste liquid container 128 Pump 129 Pipe line 130 Flow path 131 Solvent recycling device F Filter S ₁ solvent S ₂ Regeneration solvent W Waste liquid C Powdered activated carbon L Water liquid

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takao Kimura 6-21-1 Kiyoharadai, Utsunomiya-shi, Tochigi F-term (reference) 4D017 AA03 CA01 DA03 DA06 DB02 EA01

Claims (6)

[Claims] 1. A liquid chromatograph and a solvent recycling device which are combined by forming a circulation system as a whole, wherein the liquid chromatograph comprises a solvent storage tank storing a solvent, and a solvent downstream from the solvent storage tank. A pump arranged to pump the sample into a solvent, a sample injector for injecting a sample into a solvent pumped through the pump, a separation column into which a mobile phase after injecting the sample into the solvent flows, A detector for detecting a sample component in the mobile phase that has passed through the column, and at least a recorder that records a detection result by the detector, a solvent recycling device disposed between the detector and a solvent storage tank is provided. A water removal column filled with zeolite granules (molecular sieve) containing an indicator to remove water from a mobile phase introduced as waste liquid through a detector, and the water removal column A pressure-resistant distillation section formed to freely control heating at an appropriate temperature determined by a relationship with a boiling point of a solvent as a contained component in order to distill a mobile phase as a waste liquid from which water has been removed through an inert gas; A solvent recycling device characterized by comprising at least a cooling unit configured to introduce and vaporize the vapor generated in the distillation unit together with the inert gas and to cool and liquefy it as a regenerating solvent and to freely return to the solvent storage tank. A liquid chromatograph comprising: 2. The solvent storage tank includes a solvent first storage tank and a solvent second storage tank, which are arranged such that a flow path can be freely switched via a flow path switching valve. The liquid chromatograph provided with the solvent recycling device according to claim 1, wherein the storage tank is connected to a deodorizing container containing powdered activated carbon and an air check container containing water liquid in a freely breathable manner through a connecting pipe. 3. A liquid chromatograph and a solvent recycling device which are combined to form a non-circulating system as a whole, wherein the liquid chromatograph comprises: a solvent storage tank in which a solvent is stored;
A pump arranged to pump the solvent downstream from the solvent storage tank, a sample injector for injecting a sample into the solvent pumped through the pump, and a mobile phase after the sample is injected into the solvent flows into the solvent A separation column, a detector for detecting a sample component in the mobile phase passing through the separation column, a recorder for recording a detection result by the detector, and a detector via a flow path switching valve and one flow path A waste collector from which a waste liquid from a detector is introduced through the other flow path that is switched and controlled by the flow path switching valve, and the solvent storage tank. The solvent recycling device disposed in the waste liquid container is filled with zeolite granules (molecular sieve) containing an indicator to remove water from the mobile phase forcedly introduced as waste liquid from the waste liquid container. Flexible formation of heating control at an appropriate temperature determined by the relationship between the removal column and the boiling point of the solvent as a component to distill the mobile phase as waste liquid from which water has been removed through the water removal column in an inert gas. At least a pressure-resistant distillation section, and a cooling section formed by introducing steam generated in the pressure-resistant distillation section together with an inert gas to be cooled and liquefied and circulated freely as a regenerating solvent into the solvent storage tank. A liquid chromatograph comprising a solvent recycling device, comprising: 4. The solvent recycling apparatus according to claim 3, wherein the solvent storage tank is sequentially connected to a deodorizing container containing powdered activated carbon and an air check container containing water liquid through a connecting pipe so as to be freely ventilated. Liquid chromatograph equipped. 5. A pressure-resistant distillation section of the solvent recovery device, wherein the pressure-resistant distillation section has a cylindrical pressure-resistant container inclined so that waste liquid introduced through a detector flows down, and a temperature set in an internal space of the pressure-resistant container. A heater that can be turned on and off based on the relationship between the sensor and the temperature detected by the temperature sensor so that the peripheral portion including the liquid reservoir of the pressure-resistant container can be freely heated, and the supply of inert gas into the pressure-resistant container can be freely controlled. At least an inert gas supply unit, wherein the cooling unit is connected to a constant temperature block capable of maintaining a predetermined cooling temperature and a flow path derived from the pressure-resistant container, and is introduced into the constant temperature block. And at least a conduit that is arranged spirally so that at least its upstream side is located on the lower side and the downstream side is located on the upper side, and is led out into the solvent storage tank. Four A liquid chromatograph comprising the solvent recycling device according to any one of the above. 6. A regenerated solvent from which water has been removed from a used waste liquid is recovered by using a liquid chromatograph provided with the solvent recycling apparatus according to claim 1. How to collect used solvent.