JP2019111463A - Method for purifying non-aqueous liquid substance and ion exchange resin filling cartridge with exterior air shut-off member - Google Patents

Abstract

To provide a method for purifying a non-aqueous liquid substance capable of reducing a non-aqueous liquid substance mass used for an initial blow.SOLUTION: A method for purifying a non-aqueous liquid substance includes: an ion exchange resin filling step of obtaining an ion exchange resin filling cartridge 20a filled with a macroporous type or porous type ion exchange resin in a well wet state before reduction in a water content; a water content reduction step of reducing the water content of the macroporous type or porous type ion exchange resin after reduction in the water content so that the water content becomes 10.0-97.0% of the water content in a saturated equilibrium state; an initial blowing step of passing an unpurified non-aqueous liquid substance into the cartridge container 20a filled with the macroporous type or porous type ion exchange resin after reduction in the water content, and discharging an initial blow waste liquid; and a step of passing the non-aqueous liquid substance into the cartridge container 20a, and purifying the non-aqueous liquid substance.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for purifying non-aqueous liquid material for removing impurities in non-aqueous liquid material, and an ion exchange resin-filled cartridge used therefor.

  As a technique for removing trace metals in non-aqueous liquid material, an ion exchange resin is packed into a cartridge or column, and the non-aqueous liquid material as the liquid to be treated is passed directly into the cartridge or column and purified. A purification method (purification method 1) for obtaining a liquid liquid substance, and a cartridge filled with an ion exchange resin and further covering the same are provided, and a non-aqueous liquid substance to be treated passes between the cartridge and the storage container. After that, the purification method (purification method 2) is known which passes through the inside of the cartridge to obtain a purified non-aqueous liquid substance.

  As the purification method 1, for example, Patent Document 1 reports a purification method in which a non-aqueous liquid is brought into contact with a cation exchange resin having a water content of 3 to 30% to remove metal ions and the like. Patent Document 2 reports a purification method in which a non-aqueous liquid is brought into contact with a cation exchange resin having a water content of less than 3% and an anion exchange resin having a water content of 30% or less to remove metal ions and the like. ing. In Patent Document 3, a method of reducing a strongly acidic cation exchange resin to a water content of 5% or less, packing a drying ion exchange resin into a column, and purifying a non-aqueous liquid material by passing the non-aqueous liquid material Has been reported.

  As the purification method 2, for example, in Patent Document 4, as a purifier for removing chromium from an organic solvent, a purifier including an ion exchange resin container for filling an ion exchange resin in a cylindrical housing and a method of use Is reported about.

  Then, in the ion exchange resin filled cartridge before use, the ion exchange resin in a water wet state is usually filled.

  On the other hand, it is required that the non-aqueous liquid substance purified by the ion exchange resin-filled cartridge be highly purified by reducing the impurity concentration, so water and other ions become impurities as well as metal ions in the non-aqueous liquid substance. Therefore, extremely low moisture content is required.

  For example, when purifying a non-aqueous liquid having a water concentration of several hundred ppm or less, the pore inside the ion exchange resin remains in the pore by swelling in the non-aqueous liquid even if a dry ion exchange resin is used The elution of water molecules and the elution of water molecules hydrated with ion exchange groups by ion exchange increase the water concentration in the treatment liquid compared to the liquid to be treated. Therefore, in order to perform purification of non-aqueous liquid material using an unused ion exchange resin-filled cartridge, the non-aqueous liquid material is passed through the cartridge and filled in the cartridge before purification. By contacting with the ion exchange resin, it is necessary to have an initial blowing step to remove the water of the ion exchange resin.

  As a method of reducing the water content of the ion exchange resin, for example, thermal drying or reduced pressure drying reported in Patent Document 3 is used.

JP, 2004-181351, A JP, 2004-181352, A JP 2004-249238 A Publication No. 5758558

  However, in ordinary thermal drying or vacuum drying, contact with metal in the drying step and the step of transferring the dry ion exchange resin to the cartridge or column, or contact with the atmosphere containing metal or fine particles may be a problem to the ion exchange resin. There is a problem that it causes the mixing of impurities.

  Accordingly, an object of the present invention is to provide an amount of non-aqueous liquid material used for initial blow in a method of purifying non-aqueous liquid material by contacting non-aqueous liquid material with ion exchange resin to remove impurities from non-aqueous liquid material. It is an object of the present invention to provide a method of purifying a non-aqueous liquid material which can reduce the amount of water and which does not contaminate the ion exchange resin in the ion exchange resin-filled cartridge.

Such problems as described above are solved by the present invention described below.
That is, the present invention (1) is a method for purifying a non-aqueous liquid substance, which comprises removing the impurities from the non-aqueous liquid substance by bringing the non-aqueous liquid substance into contact with a macroporous or porous ion exchange resin.
The ion exchange resin is filled with an ion exchange resin-filled cartridge in which a macroporous or porous ion exchange resin in a water wet state is filled in a cartridge container and the macroporous or porous ion exchange resin is filled before the water content reduction. Process,
The water content (A) of the macroporous or porous ion exchange resin after reduction of water content is 10.0 to 97. of the water content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin. A moisture content reducing step of reducing the moisture content of the macroporous or porous ion exchange resin in the cartridge container to 0%;
The unrefined non-aqueous liquid material is passed through the cartridge container filled with the macroporous or porous ion exchange resin after the reduction of water content, and the initial blow waste solution is discharged from the cartridge container Initial blow process,
By passing the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the macroporous or porous ion exchange resin in the cartridge container, Purifying the non-aqueous liquid material to obtain a purified non-aqueous liquid material;
It provides the purification method of the non-aqueous liquid substance characterized by having.

The present invention (2) is a method for purifying a non-aqueous liquid material, which comprises removing the impurities from the non-aqueous liquid material by bringing the non-aqueous liquid material into contact with the gel type ion exchange resin,
An ion exchange resin filling step of filling a cartridge container with a gel type ion exchange resin in a water wet state and obtaining an ion exchange resin filled cartridge filled with the gel type ion exchange resin before water content reduction;
The cartridge until the water content (F) of the gel type ion exchange resin after water content reduction becomes 10.0 to 65.0% of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin A moisture content reduction step of reducing the moisture content of the gel type ion exchange resin in a container;
An initial blowing step of passing the unrefined non-aqueous liquid material into the cartridge container filled with the gel type ion exchange resin after reduction of water content and discharging an initial blow waste solution from the cartridge container; ,
By pouring the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the gel-type ion exchange resin in the cartridge container to cause the non-aqueous liquid to flow. Purifying the substance to obtain the purified non-aqueous liquid substance;
It provides the purification method of the non-aqueous liquid substance characterized by having.

Moreover, the present invention (3) is a cartridge container,
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A macroporous or porous ion exchange resin filled in the cartridge container, wherein the water content (D) is 10.0 to 97.0% of the water content (E) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an external air blocking member, characterized in that

Also, the present invention (4) is a cartridge container,
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A gel type ion exchange resin filled in the cartridge container and having a water content (I) of 10.0 to 65.0% of a water content (J) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an external air blocking member, characterized in that

  According to the present invention, in the method of purifying a non-aqueous liquid material, the non-aqueous liquid material is brought into contact with an ion exchange resin to remove impurities from the non-aqueous liquid material, the amount of non-aqueous liquid material used for initial blowing is reduced. It is possible to provide a method of purifying a non-aqueous liquid which can be carried out and the ion exchange resin in the ion exchange resin filled cartridge is not contaminated.

It is an end elevation which shows the embodiment of the ion exchange resin filling cartridge of this invention. It is a perspective view which shows each member which comprises the ion exchange resin cartridge 20a in FIG. It is a typical end elevation which shows a mode that the initial stage blowing process is performed. It is a typical end elevation which shows a mode that the refinement | purification process is performed. It is a typical end elevation which shows the embodiment of an ion exchange resin filling cartridge. It is a typical end elevation which shows the embodiment of the ion exchange resin filling cartridge with the external air blocking member of this invention. It is a graph which shows the result of Example 1, Example 2, and the comparative example 1. FIG. It is a graph which shows the result of Example 3, Example 4, Comparative Example 2, and Comparative Example 3.

  The purification method of the non-aqueous liquid substance of the present invention will be described with reference to FIGS. 1 to 4. FIG. 1 is a schematic end view showing an embodiment of an ion exchange resin-filled cartridge used in the method for purifying non-aqueous liquid material of the present invention, wherein the ion exchange resin-filled cartridge after performing the ion exchange resin filling step FIG. FIG. 2 is a perspective view showing members constituting the ion exchange resin-filled cartridge 20 a in FIG. 1. FIG. 3 is a schematic end view showing how an initial blowing process is being performed. FIG. 4 is a schematic end view showing how the purification step is being performed.

  The ion exchange resin-filled cartridge 20a shown in FIG. 1 is a cartridge exchangeably attached to a metal removal column for removing metal in the non-aqueous liquid material with the ion exchange resin. The ion exchange resin filled cartridge 20a includes a cylindrical part 2 filled with granular macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in a water wet state, a liquid to be treated (unrefined non-purified) A through hole 7 for the liquid substance is formed, an upper lid 3 provided at the upper end of the cylindrical portion 2 and a through hole 8 for the treatment liquid (non-aqueous liquid substance after purification) are formed. The lower lid 4 provided at the lower end of the metal pipe, the insertion pipe 5 connected to the lower lid and inserted inside the treatment liquid discharge pipe provided at the bottom of the metal removal column storage container, and the inside of the cylindrical portion 2 And granular macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a filled therein. An O-ring attachment groove 51 is formed on the outside of the insertion pipe 5 to seal between the inner wall of the treatment liquid discharge pipe of the metal removal column and the outside of the insertion pipe 5 of the ion exchange resin-filled cartridge 20a. There is. The O-ring 6 is fitted and attached to the O-ring attachment groove 51. In the embodiment shown in FIG. 1, the lower cover 4 and the insertion tube 5 are integrally formed. Further, in the embodiment shown in FIG. 1, the lower lid 4 to which the cylindrical portion 2, the upper lid 3 and the insertion tube 5 are attached is a cartridge container. Further, the upper end side tube diameter reduction portion 11 is formed on the upper end side inside the cylindrical portion 2, and the lower end side tube diameter reduction portion 12 is formed on the lower end side inside the cylindrical portion 2 There is. And in order to prevent the macroporous type or porous type ion exchange resin (or gel type ion exchange resin) 1a from flowing out from the cylindrical portion 2, a mesh 9 is provided at the upper end of the filling region of the ion exchange resin. An outer edge portion is attached by being pinched between the side tube diameter reduced portion 11 and the upper lid 3, and the mesh 10 is attached to the lower end of the ion exchange resin filled region, the lower tube diameter reduced portion 12 and the upper lid An outer edge portion is attached by being sandwiched between 4 and 5. The mesh 9 and the mesh 10 have a gap of such a size that the liquid to be treated can be permeated and the granular macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a can not permeate.

  As shown in FIG. 2, in the assembly of the ion exchange resin-filled cartridge 20 a, first, the lower lid 4 integrally formed with the insertion tube 5 in a state where the mesh 10 is disposed inside the lower end of the cylindrical portion 2, Screw it into the lower end of 2 and insert it. At this time, the outer edge portion of the mesh 10 is sandwiched and fixed between the lower end side tube diameter reduction portion 12 and the lower lid 4. Next, the tubular portion 2 is filled with granular macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a (not shown) in a water wet state. Next, with the mesh 9 disposed inside the upper end of the cylindrical portion 2, the upper cover 3 is screwed into the upper end side of the cylindrical portion 2 and fitted. At this time, the outer edge portion of the mesh 9 is sandwiched and fixed between the upper end side tube diameter reduction portion 11 and the upper lid 3. Next, the O-ring 6 is attached to the O-ring attachment groove 51 formed in the insertion pipe 5.

  Then, by performing the ion exchange resin filling step, an ion exchange resin filled cartridge in which a macroporous or porous ion exchange resin (or gel type ion exchange resin) in a water wet state is filled in the cartridge container is manufactured. .

  Subsequently, the ion exchange resin filled cartridge 20a obtained by performing the ion exchange resin filling step, that is, the cartridge container is filled with a macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in a water wet state The water content reduction step is performed using the ion exchange resin-filled cartridge 20a. First, the ion exchange resin-filled cartridge 20a in which a macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in a water-wet state is filled in a cartridge container is allowed to stand in a reduced pressure drying apparatus. Next, the inside of the reduced pressure drying apparatus is depressurized, and after reaching a predetermined degree of reduced pressure, the macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in a wet state is heated for each cartridge container to reduce the pressure. dry. At this time, evaporation of water proceeds from the surface of the macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in the water wet state to the inside from the vicinity thereof, and the macroporous type of the water wet state or The moisture content of the porous ion exchange resin (or gel type ion exchange resin) 1a is reduced. Then, the macroporous or porous ion exchange resin in water wet state until the water content of the macroporous or porous ion exchange resin (or gel type ion exchange resin) 1a in water wet state becomes a predetermined water content (Or gel type ion exchange resin) 1a is dried under reduced pressure to convert it into macroporous or porous ion exchange resin (or gel type ion exchange resin) 1b after the water content reduction which is a predetermined water content. Thus, by performing the water content reduction step, the cartridge container is filled with the ion exchange resin filled with the macroporous or porous ion exchange resin (or gel type ion exchange resin) 1 b after the water content reduction. Make the cartridge 20b.

  Next, as shown in FIG. 3, the ion exchange resin-filled cartridge 20b obtained by performing the water content reduction step is installed in the storage container 21 of the metal removal column 30, and the metal removal column 30 is assembled. The metal removal column 30 is formed in the storage container 21 and the storage container 21 and has a liquid supply port 22 for supplying the liquid to be treated (unrefined non-aqueous liquid substance) to the inside of the storage container, and the storage container A treatment liquid discharge pipe 23 provided on the bottom side of the container 21 and communicating with the inside of the storage container 21 for discharging the processing liquid (non-aqueous liquid substance after purification), and ions stored in the storage container 21 And a replacement resin filled cartridge 20b. Then, the insertion pipe 5 of the ion exchange resin-filled cartridge 20b is inserted into the inside of the processing liquid discharge pipe 23, and the O-ring 6 attached to the outside of the insertion pipe 5 is the inner wall 24 of the processing liquid discharge pipe 23 and the ions. By adhering closely to the outside of the insertion pipe 5 of the replacement resin-filled cartridge 20, the space between the inner wall of the treatment liquid discharge pipe 23 and the outside of the insertion pipe 5 is sealed. Further, a connection pipe 28 is attached to the liquid supply port 22. Then, the end of the infusion pipe 26 of the liquid to be treated (unrefined non-aqueous liquid substance) 31 is screwed into the connection pipe 28, and the infusion pipe 26 of the liquid to be treated (non-aqueous liquid substance after purification) 31 Is connected. Further, the end of the infusion tube 25 of the treatment liquid is screwed into the treatment liquid discharge tube 23, and the infusion tube 25 of the treatment liquid is connected. In addition, a discharge pipe (not shown) of the initial blow waste fluid 311 branched from the infusion pipe 25 for the treatment liquid is attached to the treatment liquid infusion tube 25 in order to discharge the initial blow waste fluid 311 to the outside.

Next, the liquid to be treated (unrefined non-aqueous liquid substance) 31 is transferred from the storage tank of the liquid to be treated 31 to the metal removal column 30 through the infusion tube 26 of the liquid to be treated connected to the metal removal column 30. The liquid is carried and supplied into the storage container 21 of the metal removal column 30 via the liquid supply port 22. Then, first, the space 27 between the cylindrical portion 2 of the ion exchange resin-filled cartridge 20 b and the storage container 21 of the metal removal column 30 is filled with the liquid to be treated 31 supplied into the storage container 21. The resin filling cartridge 20b is made to flow into the cartridge container of the ion exchange resin filling cartridge 20b through the passage hole 7 of the liquid to be treated formed in the upper lid 3 of the resin filling cartridge 20b. Next, the liquid to be treated 31 allowed to flow into the cartridge container of the ion exchange resin-filled cartridge 20b is brought into contact with the macroporous or porous ion exchange resin (or gel ion exchange resin) 1b filled in the cartridge container. The cartridge of the ion exchange resin filled cartridge 20b is passed through the filled area of the ion exchange resin while passing through and through the passage holes (reference numeral 8 in FIG. 1) of the treatment liquid formed in the lower lid 4 of the cylindrical portion 2. Drain out of the container. The initial blow waste solution 311 discharged out of the cartridge container of the ion exchange resin-filled cartridge 20 b is discharged from the initial blow waste solution discharge pipe branched from the infusion solution pipe 25 of the treatment liquid connected to the metal removal column 30. At this time, the transfer valve of the initial blow waste solution 311 is initially operated by operating the switching valve attached to the infusion tube 25 of the treatment liquid so that the initial blow waste solution does not flow into the use point or the storage tank of the treatment liquid. Switch to the blow waste liquid discharge pipe side. Then, until the water concentration (mg H ₂ O / g non-aqueous liquid substance) in the initial blow waste solution 311 reaches a predetermined concentration, or until the initial initial blow amount reaches a predetermined value, the macroporous type after water content reduction The contact between the porous ion exchange resin (or gel type ion exchange resin) 1 b and the liquid to be treated (unrefined non-aqueous liquid substance) 31 is continued. It is desirable to analyze the water concentration in the non-aqueous liquid substance by Karl Fischer coulometric titration method.

  Thus, by performing the initial blowing step, the macroporous or porous ion exchange resin (or gel type ion exchange resin) can be treated with the macroporous or porous ion exchange resin (or gel type ion after the initial blowing). Exchange resin) converted to 1c.

  Next, the transfer valve of the treatment liquid is operated to switch the transport path of the treatment liquid to the use point or the storage tank side of the treatment liquid, as shown in FIG. The liquid (unrefined non-aqueous liquid substance) 31 is carried from the storage tank of the liquid 31 to be treated to the metal removal column 30 through the infusion pipe 26 of the liquid to be treated connected to the metal removal column 30. The liquid is supplied into the storage container 21 of the metal removal column 30 through the liquid supply port 22. Then, first, the liquid 27 supplied into the storage container 21 is allowed to pass through the space 27 between the cylindrical portion 2 of the ion exchange resin-filled cartridge 20 c and the storage container 21 of the metal removal column 30. The resin filling cartridge 20c is made to flow into the cartridge container of the ion exchange resin filling cartridge 20c through the passage hole 7 of the liquid to be treated formed in the upper lid 3 of the resin filling cartridge 20c. Next, the liquid to be treated 31 allowed to flow into the cartridge container of the ion exchange resin-filled cartridge 20c is brought into contact with the macroporous or porous ion exchange resin (or gel ion exchange resin) 1c filled in the cartridge container. The cartridge of the ion exchange resin filled cartridge 20c is passed through the filling area of the ion exchange resin while passing through, and through the passage hole (reference numeral 8 in FIG. 1) of the treatment liquid formed in the lower lid 4 of the cylindrical portion 2. Drain out of the container. The treatment liquid (refined non-aqueous liquid substance) 32 discharged to the outside of the cartridge container of the ion exchange resin-filled cartridge 20 c is used at the point of use or treatment via the treatment liquid infusion tube 25 connected to the metal removal column 30. Transport to the storage tank of liquid. Thus, the purification process is carried out to obtain the non-aqueous liquid substance after purification.

The purification method of the non-aqueous liquid material according to the first aspect of the present invention is a non-aqueous liquid material which removes impurities from the non-aqueous liquid material by bringing the non-aqueous liquid material into contact with a macroporous or porous ion exchange resin. A purification method,
The ion exchange resin is filled with an ion exchange resin-filled cartridge in which a macroporous or porous ion exchange resin in a water wet state is filled in a cartridge container and the macroporous or porous ion exchange resin is filled before the water content reduction. Process,
The water content (A) of the macroporous or porous ion exchange resin after reduction of water content is 10.0 to 97. of the water content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin. A moisture content reducing step of reducing the moisture content of the macroporous or porous ion exchange resin in the cartridge container to 0%;
The unrefined non-aqueous liquid material is passed through the cartridge container filled with the macroporous or porous ion exchange resin after the reduction of water content, and the initial blow waste solution is discharged from the cartridge container Initial blow process,
By passing the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the macroporous or porous ion exchange resin in the cartridge container, Purifying the non-aqueous liquid material to obtain a purified non-aqueous liquid material;
It is a purification method of a non-aqueous liquid substance characterized by having.

In the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, an ion exchange resin is brought into contact with an unrefined non-aqueous liquid material as a liquid to be treated to remove impurities from the unrefined non-aqueous liquid material Method for purifying non-aqueous liquid material. In the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the purification target is an unrefined non-aqueous liquid material. Unrefined non-aqueous liquid substances, ie, liquid to be treated include IPA (isopropanol), PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), PGEE (propylene glycol monoethyl ether), NMP (N Organic solvents such as -methyl-2-pyrrolidone) can be mentioned. As impurities in the unrefined non-aqueous liquid substance, metal ions such as Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd, Pb, etc. Anions such as Cl, SO ₄ , NO ₃ , PO ₄ , CO ₃ , HCO ₃ , etc., organic acids such as formic acid, acetic acid, maleic acid, proponic acid, etc., and polymer compounds having positive to negative charges.

  In the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the ion exchange resin used to purify the non-aqueous liquid material is a particulate macroporous or porous ion exchange resin. As macroporous or porous ion exchange resin, macroporous or porous cation exchange resin, macroporous or porous anion exchange resin, macroporous or porous cation exchange resin, and macroporous or porous anion exchange The combination of resin is mentioned. When the macroporous or porous ion exchange resin is a combination of a macroporous or porous cation exchange resin and a macroporous or porous anion exchange resin, the macroporous or porous cation exchange resin and the macroporous or porous are used. When used as a mixed bed in which the anion-type anion exchange resin is uniformly mixed, the macroporous-type or porous-type cation exchange resin is filled on the upstream side of the filling region of the macroporous-type or porous type ion exchange resin, The downstream side of the macroporous or porous ion exchange resin-filled region is filled with the macroporous or porous anion exchange resin, or the upstream side of the macroporous or porous ion exchange resin-filled region, Macroporous type or porous type On-exchange resin is filled, and, on the downstream side of the filling region of the macroporous type or porous type ion exchange resin, is sometimes used as Fukuyuka that macroporous or porous type cation-exchange resin is filled.

  The macroporous or porous cation exchange resin is a combination of a macroporous or porous strong acid cation exchange resin or a macroporous or porous weak acid cation exchange resin. May be As the macroporous or porous strong acid cation exchange resin, Orlite DS-4 and the like can be mentioned. Further, as the macroporous or porous weak acid cation exchange resin, Amberlite IRC 76, Amberlite IRC 747, Amberlite IRC 748, etc. may be mentioned.

  The macroporous or porous anion exchange resin is a combination of a macroporous or porous strong base anion exchange resin or a macroporous or porous weak base anion exchange resin. It may be As a macroporous or porous strong base anion exchange resin, Orlite DS-5 and the like can be mentioned. Moreover, as the macroporous or porous weakly basic anion exchange resin, Orlite DS-6 and the like can be mentioned.

  The average particle size of the dry macroporous or porous ion exchange resin is not particularly limited, but is preferably 200 to 1000 μm, and particularly preferably 400 to 800 μm. The average particle size of the dry macroporous or porous ion exchange resin is a value measured by a laser diffraction type particle size distribution measuring apparatus.

  The macroporous or porous ion exchange resin is usually produced in a water-containing state, and is present in a water-containing state even at the time of sales, distribution, filling of the ion exchange resin at the place of use, etc. There is. In the present invention, the macroporous or porous ion exchange resin in a water-containing state is referred to as "water-wet macroporous or porous ion exchange resin", and the water-wet state is 25 ° C. The state in which the water content is saturated at a relative humidity of 100% in is referred to as "a macroporous or porous ion exchange resin in a saturated equilibrium state". The state of being dried by an appropriate drying method and having a water content of 0% by mass is referred to as "dry state macroporous or porous ion exchange resin".

The macroporous or porous ion exchange resin in a saturated equilibrium state can be obtained by bringing the macroporous or porous ion exchange resin into saturation by bringing it into contact with air at 25 ° C. and 100% relative humidity for 30 minutes or longer. . The macroporous or porous ion exchange resin in a dry state can be obtained by drying the macroporous or porous ion exchange resin in a water wet state by a constant temperature drier at 105 ° C. for 16 hours. The water content (%) (B) of the macroporous or porous ion exchange resin in the saturated equilibrium state is “((weight of the macroporous or porous ion exchange resin in the saturated equilibrium state before drying-dried macro The weight of the porous or porous ion exchange resin) / the weight of the macroporous or porous ion exchange resin in a saturated equilibrium state before drying) × 100 ”. The amount of the macroporous or porous ion exchange resin in a saturated equilibrium state before drying is preferably 5 g or more in order to enhance the measurement accuracy.
Similarly, for the water content (%) (A) of the macroporous or porous ion exchange resin after the water content reduction, at least 5 g of the resin to be measured is weighed out, and the weighed resin is taken with a thermostatic oven at 105 ° C. After drying for 16 hours, (((weight of macroporous or porous ion exchange resin after reduction of water content-weight of macroporous or porous ion exchange resin in dry state) / macroporous after reduction of water content) The weight of the porous ion exchange resin can be obtained by the following formula.
Also, for the water content (%) (C) of the macroporous or porous ion exchange resin before the water content reduction, similarly, weigh 5 g or more of the resin to be measured, and use the constant temperature drier 105 for the weighed resin. "((Weight of macroporous or porous ion exchange resin before reduction of water content-weight of macroporous or porous ion exchange resin in dry state) before drying for 16 hours, macroporous before reduction of water content Weight of mold or porous type ion exchange resin) × 100 ".

  In the ion exchange resin filling step according to the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, a macroporous or porous ion exchange resin in a water wet state is filled in a cartridge container, This is a step of obtaining an ion exchange resin-filled cartridge filled with a porous or porous ion exchange resin.

  The cartridge container according to the ion exchange resin filling step of the method for purifying a non-aqueous liquid material according to the first aspect of the present invention is an ion exchange resin filled with a macroporous or porous ion exchange resin in water wet state. It is a filling container. The cartridge container is not particularly limited, and may be appropriately selected depending on, for example, the shape of the metal removal column on which the ion exchange resin-filled cartridge is installed, but generally, the cylindrical member and both ends of the cylindrical member are selected. And a lid member for closing. At one end of the cartridge container, a treatment liquid supply port for supplying unrefined non-aqueous liquid substance (liquid to be treated) into the cartridge container is formed, and at the other end of the cartridge container In this case, a liquid discharge port for discharging the non-aqueous liquid substance (treatment liquid) after purification from the inside of the cartridge container is formed.

  The material of the cartridge container is not particularly limited. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA) tetrafluoroethylene-ethylene copolymer (ETFE), low density polyethylene And high density polyethylene. The material of the cartridge container is appropriately selected depending on the type of liquid to be treated, the type of dissolved substance, and the like.

  In the ion exchange resin filling step of the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the ion exchange resin filled in the cartridge container is a water wet ion exchange resin. In the ion exchange resin filling step, the water content of the macroporous or porous ion exchange resin in a water wet state filled in the cartridge container, that is, the water content of the macroporous or porous ion exchange resin before the water content reduction (C) Is preferably 95 to 100%, particularly preferably 98 to 100%, of the water content (B) in a saturated equilibrium state of the macroporous or porous ion exchange resin. Usually, the water content of the macroporous or porous ion exchange resin manufactured industrially is 95 to 100% of the water content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin, and The water content of the commercially available macroporous or porous ion exchange resin is 95 to 100% of the water content (B) in the saturated equilibrium state of the macroporous or porous ion exchange resin. Therefore, in the ion exchange resin filling step, industrially manufactured macroporous or porous ion exchange resin in a water wet state, or commercially available macroporous or porous ion exchange resin in a water wet state is preferable. Used for “The moisture content (C) of the macroporous or porous ion exchange resin in the water-wet state is preferably 95 to 100% of the moisture content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin (Particularly preferably 98 to 100%) is “a macroporous or porous ion exchange resin in a water wet state actually filled in the ion exchange resin filling step, ie, macroporous before reduction of water content The percentage calculated by the moisture content (C) of the porous or porous ion exchange resin / "water content in saturated equilibrium state of macroporous or porous ion exchange resin (B)" x 100 is preferably 95 to It refers to 100%, particularly preferably 98 to 100%.

  In the ion exchange resin filling step of the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the method for filling the ion exchange resin in a water wet state in the cartridge container is not particularly limited. The method which does not mix is selected suitably.

  The ion exchange resin-filled cartridge obtained by performing the ion exchange resin filling step of the method for purifying non-aqueous liquid material according to the first aspect of the present invention is a macroporous or porous ion exchange resin in a water-wet state in a cartridge container. Is an ion exchange resin filled cartridge filled with Since the ion exchange resin filled cartridge obtained by performing the ion exchange resin filling process is an ion exchange resin filled cartridge before the water content reduction process, the ion exchange resin filled process obtained by performing the ion exchange resin filling process In other words, the cartridge is an ion exchange resin-filled cartridge in which the cartridge container is filled with the macroporous or porous ion exchange resin before reduction of the water content.

  In the water content reduction step according to the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the water content (A) of the macroporous or porous ion exchange resin after the water content reduction is macroporous or porous To 90.0%, preferably 10.0% to 90.0%, of the moisture content (B) of the saturated ion exchange resin in the saturated equilibrium state, the macroporous or porous type in the cartridge container This is a step of reducing the water content of the ion exchange resin. “The moisture content (A) of the macroporous or porous ion exchange resin after reduction of the moisture content is 10.0 to 97 of the moisture content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin .0%, preferably 10.0% or more and less than 90.0% ("The moisture content of the macroporous or porous ion exchange resin after the moisture content reduction in the moisture content reduction step (A) The percentage calculated by “water content in saturated equilibrium state of macroporous type or porous type ion exchange resin (B)” × 100 is 10.0 to 97.0%, preferably 10.0% to 90%. It means that it will be less than .0%.

  In the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, an inert gas is passed through the inside of the cartridge container to bring the macroporous or porous ion exchange resin in the cartridge container into contact with the inert gas. Thus, the water content reduction step (hereinafter, such a form is also described as the water content reduction step (A1)) can be performed.

  Nitrogen gas, helium gas, argon gas etc. are mentioned as an inert gas which concerns on a moisture content reduction process (A1). The purity of the inert gas is preferably as high as possible, but it may be 99.9% by volume or more. The dew point of the inert gas is preferably −50 ° C. or less, particularly preferably −60 ° C. or less.

  In the water content reduction step (A1), when the ion exchange resin filled in the cartridge container is only a cation exchange resin, the temperature of the inert gas when supplying the inert gas into the cartridge container is preferably 0. It is -120 ° C, particularly preferably 60-110 ° C. In the water content reduction step (A1), when the ion exchange resin filled in the cartridge container is only anion exchange resin or a combination of cation exchange resin and anion exchange resin, an inert gas is contained in the cartridge container. The temperature of the inert gas when fed is preferably 0 to 60 ° C., particularly preferably 30 to 50 ° C.

  In the water content reduction step (A1), when the inert gas contacts the water-wet macroporous or porous ion exchange resin, the water of the water-wet macroporous or porous ion exchange resin is evaporated Then, the moisture content of the macroporous or porous ion exchange resin in a water-wet state is reduced by transferring to an inert gas. At this time, evaporation of water proceeds from the water present on the surface of the macroporous or porous ion exchange resin in the water wet state and in the vicinity thereof to the inside.

  In the water content reduction step (A1), the water content (A) of the macroporous or porous ion exchange resin after the water content reduction is the water content of the macroporous or porous ion exchange resin in the saturated equilibrium state ((A)) Continue to keep the inert gas in contact with the macroporous or porous ion exchange resin in a water-wet state until it becomes 10.0 to 97.0%, preferably 10.0% or more and less than 90.0% of B). A macroporous or porous ion exchange resin in a water wet state is converted to a macroporous or porous ion exchange resin after reduction of the water content, which is a predetermined water content.

  In the water content reduction step (A1), the method of passing the inert gas through the cartridge container and bringing the macroporous or porous ion exchange resin in the cartridge container into contact with the inert gas is not particularly limited. The method may be any method as long as the inert gas is supplied from the one end side of the cartridge container into the cartridge container and the inert gas is discharged from the inside of the cartridge container from the other end side of the cartridge container.

  In the water content reduction step (A1), the inert gas containing the water in the macroporous or porous ion exchange resin is treated with the inert gas dehydrator to control the water content in the inert gas. It can be reduced and used again as the inert gas supplied into the cartridge container in the water content reduction step (A1).

  Further, in the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, the water content reduction step (hereinafter referred to as “the water content reduction step”) Such a form can be performed also as a moisture content reduction process (A2).

  In the water content reduction step (A2), the absolute pressure at the time of drying under reduced pressure is preferably -0.05 MPa or less. In the water content reduction step (A2), when the ion exchange resin filled in the cartridge container is only a cation exchange resin, the temperature for drying under reduced pressure is preferably 0 to 120 ° C., particularly preferably 60 to 110 ° C. It is. In the water content reduction step (A2), when the ion exchange resin filled in the cartridge container is only an anion exchange resin or a combination of a cation exchange resin and an anion exchange resin, the temperature when drying under reduced pressure is It is preferably 0 to 60 ° C, particularly preferably 30 to 50 ° C. A well-known vacuum dryer may be used to place the resin to be treated under the above-described heating and reduced pressure drying conditions.

  In the water content reduction step (A2), the water of the macroporous or porous ion exchange resin in the water wet state is evaporated by drying the macroporous or porous ion exchange resin of the water wet state under reduced pressure, and water is removed. The moisture content of the wet macroporous or porous ion exchange resin is reduced. At this time, evaporation of water proceeds from the water present on the surface of the macroporous or porous ion exchange resin in the water wet state and in the vicinity thereof to the inside.

  In the water content reduction step (A2), the water content (A) of the macroporous or porous ion exchange resin after the water content reduction is the water content of the macroporous or porous ion exchange resin in a saturated equilibrium state ((A)) Under reduced pressure drying of the macroporous or porous ion exchange resin in the water wet state to 10.0 to 97.0%, preferably 10.0% to 90.0% of B), the water wet state The macroporous or porous ion exchange resin is converted to a macroporous or porous ion exchange resin having a predetermined water content after reduction of the water content.

  The method for drying the macroporous or porous ion exchange resin in a water-wet state under reduced pressure in the water content reduction step (A2) is not particularly limited. For example, the ion exchange resin filled cartridge is allowed to stand in a reduced pressure drying device There is also a method in which the inside of the reduced-pressure drying apparatus is decompressed, or the inside of the reduced-pressure drying apparatus is decompressed and heated to perform the reduced-pressure drying. When the inside of the reduced-pressure drying apparatus is returned to normal pressure after drying under reduced pressure, it is preferable that the pressure be reduced to normal pressure by introducing an inert gas of high purity into the pressure reducing apparatus so that impurities in the atmosphere do not mix. .

  Further, in the method for purifying a non-aqueous liquid material according to the first aspect of the present invention, an ion exchange resin-filled cartridge filled with a macroporous or porous ion exchange resin is heated in a heating device under an inert gas atmosphere. Accordingly, the water content reduction step (hereinafter, such a form is also described as the water content reduction step (A3)) can be performed.

  In the water content reduction step (A3), when the ion exchange resin with which the cartridge container is filled is only a cation exchange resin, the heating temperature when heating the ion exchange resin filled cartridge is preferably 0 to 120 ° C., particularly Preferably it is 60-110 degreeC. In the water content reduction step (A3), when the ion exchange resin filled in the cartridge container is only anion exchange resin or a combination of cation exchange resin and anion exchange resin, the ion exchange resin filled cartridge is heated. The heating temperature is preferably 0 to 60 ° C., particularly preferably 30 to 50 ° C.

  In the water content reduction step (A3), the water of the macroporous or porous ion exchange resin in the water wet state is evaporated by heating the macroporous or porous ion exchange resin of the water wet state, and the water is wetted. The moisture content of the macroporous or porous ion exchange resin in the state is reduced. At this time, evaporation of water proceeds from the water present on the surface of the macroporous or porous ion exchange resin in the water wet state and in the vicinity thereof to the inside.

  In the water content reduction step (A3), the water content (A) of the macroporous or porous ion exchange resin after the water content reduction is the water content of the macroporous or porous ion exchange resin in a saturated equilibrium state ((A)) Heating the ion exchange resin in the water wet state to 10.0 to 97.0%, preferably 10.0% or more and less than 90.0% of B), the macroporous or porous type of the water wet state The ion exchange resin is converted to a macroporous or porous ion exchange resin after the water content reduction, which is a predetermined water content.

  The method for heating the water-wet macroporous or porous ion exchange resin in the water content reduction step (A3) is not particularly limited, and the ion exchange resin filled cartridge may be heated in an inert gas atmosphere heating apparatus. Any method can be used as long as it can be heated.

  Thus, by performing the water content reduction step according to the method of purifying the non-aqueous liquid material of the first aspect of the present invention, the macroporous or porous ion exchange resin in a water wet state (before the water content reduction) The macroporous or porous ion exchange resin is converted to a macroporous or porous ion exchange resin (macroporous or porous ion exchange resin after the reduction of the water content), the water content of which is a predetermined value, An ion exchange resin-filled cartridge is obtained in which the cartridge container is filled with the macroporous or porous ion exchange resin after reduction of the water content. Then, in the water content reduction step, the degree of reduction of the water content is determined by the fact that the water content (A) of the macroporous or porous ion exchange resin after reduction of water content is the saturation equilibrium of the macroporous or porous ion exchange resin Moisture content reduction step (A1), moisture content reduction step (A1) by setting the water content in the state to 10.0 to 97.0%, preferably 10.0% or more and less than 90.0%. A2) The water content can be reduced by a simple method such as the water content reduction step (A3), and the amount of the initial blow waste solution can be reduced. On the other hand, if the water content (A) of the macroporous or porous ion exchange resin after reduction of the water content relative to the water content (B) of the macroporous or porous ion exchange resin in the saturated equilibrium state exceeds the above range, The amount of initial blow waste solution will increase. If the water content (A) of the macroporous or porous ion exchange resin after reduction of the water content relative to the water content (B) in the saturated equilibrium state of the macroporous or porous ion exchange resin is less than the above range, Although the amount of the initial blow waste solution decreases, the time taken to reduce the water content of the macroporous or porous ion exchange resin becomes longer or the cost becomes higher.

  In the method of purifying the non-aqueous liquid material according to the first aspect of the present invention, the initial blowing step comprises: unrefined non-refined non-refined in a cartridge container filled with macroporous or porous ion exchange resin after water content reduction. The process is a step of passing a liquid liquid and discharging the initial blow waste solution from the cartridge container.

  The initial blowing step according to the method for purifying a non-aqueous liquid material according to the first aspect of the present invention is a pretreatment step performed before the non-aqueous liquid material is purified, and is mainly a macroporous or porous ion exchange resin Water content is replaced with non-aqueous liquid material to reduce the moisture content, and normal purification can be performed by reducing the amount of water eluted from the macroporous or porous ion exchange resin to the non-aqueous liquid material. Done for the purpose of

  Then, in the initial blowing step according to the method for purifying a non-aqueous liquid material of the first aspect of the present invention, the macroporous or porous ion exchange resin after reduction of water content until the ion exchange filled cartridge is in a predetermined state. Continue to flow unrefined non-aqueous liquid material into the cartridge container filled with. At this time, an initial blow waste solution is generated.

  In the purification process according to the first aspect of the method for purifying a non-aqueous liquid material of the present invention, an unpurified non-aqueous liquid material is passed through a cartridge container of an ion exchange resin-filled cartridge subjected to an initial blowing step. In this process, the macroporous or porous ion exchange resin in the cartridge container is brought into contact with an unrefined non-aqueous liquid substance to purify the non-aqueous liquid substance to obtain a purified non-aqueous liquid substance .

  Then, by performing the purification step according to the method for purifying a non-aqueous liquid material of the first embodiment of the present invention, a high-purity non-aqueous liquid material from which impurities have been removed can be obtained.

The purification method of the non-aqueous liquid material according to the second aspect of the present invention is a purification method of the non-aqueous liquid material, wherein the non-aqueous liquid material is brought into contact with the gel type ion exchange resin to remove impurities from the non-aqueous liquid material. ,
An ion exchange resin filling step of filling a cartridge container with a gel type ion exchange resin in a water wet state and obtaining an ion exchange resin filled cartridge filled with the gel type ion exchange resin before water content reduction;
The cartridge until the water content (F) of the gel type ion exchange resin after water content reduction becomes 10.0 to 65.0% of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin A moisture content reduction step of reducing the moisture content of the gel type ion exchange resin in a container;
An initial blowing step of passing the unrefined non-aqueous liquid material into the cartridge container filled with the gel type ion exchange resin after reduction of water content and discharging an initial blow waste solution from the cartridge container; ,
By pouring the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the gel-type ion exchange resin in the cartridge container to cause the non-aqueous liquid to flow. Purifying the substance to obtain the purified non-aqueous liquid substance;
It is a purification method of a non-aqueous liquid substance characterized by having.

  In the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, an ion exchange resin is brought into contact with an unrefined non-aqueous liquid material as a liquid to be treated to remove impurities from the unrefined non-aqueous liquid material. Method for purifying non-aqueous liquid material. In the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the purification target is an unrefined non-aqueous liquid material. The unrefined non-aqueous liquid material (liquid to be treated) and the impurities in the unrefined non-aqueous liquid material according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention are those of the first aspect of the present invention. It is the same as the impurities in the unrefined non-aqueous liquid material (to-be-treated liquid) and the unrefined non-aqueous liquid material according to the purification method of the non-aqueous liquid substance.

  In the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the ion exchange resin used to purify the non-aqueous liquid material is a particulate gel type ion exchange resin. Examples of gel type ion exchange resins include gel type cation exchange resins, gel type anion exchange resins, and combinations of gel type cation exchange resins and gel type anion exchange resins. When the gel-type ion exchange resin is a combination of a gel-type cation exchange resin and a gel-type anion exchange resin, the gel-type ion exchange resin is used as a mixed bed in which the gel-type cation exchange resin and the gel-type anion exchange resin are uniformly mixed. A gel-type cation exchange resin is filled on the upstream side of the filling region of the ion exchange resin, and a gel-type anion exchange resin is filled on the downstream side of the filling region of the gel-type ion exchange resin When used as a composite bed in which a gel type anion exchange resin is filled on the upstream side of the filling area of the exchange resin, and a gel type cation exchange resin is filled on the downstream side of the filling area of the gel type ion exchange resin is there.

  The gel-type cation exchange resin may be a gel-type strong acid cation exchange resin, a gel-type weak acid cation exchange resin, or a combination thereof. As a gel type strong acid cation exchange resin, Orlite DS-1 etc. are mentioned. Moreover, as a gel type weakly acidic cation exchange resin, Amberlite IRC 84 SPI H etc. are mentioned.

  The gel type anion exchange resin may be a gel type strong base anion exchange resin, a gel type weak base anion exchange resin, or a combination thereof. As a gel type strong base anion exchange resin, Orlite DS-2 etc. are mentioned. Moreover, as a gel type weak base anion exchange resin, Amberlite IRA 67, Amberlite IRA 70 RF, etc. may be mentioned.

  The average particle size of the gel-type ion exchange resin in a dry state is not particularly limited, but is preferably 200 to 1000 μm, and particularly preferably 400 to 800 μm. The average particle size of the gel-type ion exchange resin in a dry state is a value measured by a laser diffraction type particle size distribution measuring apparatus.

  The gel-type ion exchange resin is usually produced in a water-containing state, and is present in a water-containing state even at the time of sales, distribution, filling of the ion exchange resin at a place of use, or the like. And, in the present invention, the gel type ion exchange resin containing water is referred to as "gel type ion exchange resin in water wet state" and in the state of 100% relative humidity at 25 ° C in the water wet state. The state when the water content is saturated is referred to as "a gel type ion exchange resin in a saturated equilibrium state". The state of being dried by an appropriate drying method and having a water content of 0% by mass is referred to as "dry gel type ion exchange resin".

The gel type ion exchange resin in a saturated equilibrium state is obtained by bringing the gel type ion exchange resin into saturation by bringing it into contact with an atmosphere of 100% relative humidity at 25 ° C. for 30 minutes or more. The gel-type ion exchange resin in a dry state can be obtained by drying the gel-type ion exchange resin in a water-wet state with a constant temperature drier at 105 ° C. for 16 hours. The water content (%) (G) of the gel type ion exchange resin in the saturated equilibrium state is “((weight of gel type ion exchange resin in the saturated equilibrium state before drying-weight of the gel type ion exchange resin in the dry state) / The weight of the gel-type ion exchange resin in a saturated equilibrium state before drying is determined by the equation of 100). The amount of gel-type ion exchange resin collected in a saturated equilibrium state before drying is preferably 5 g or more in order to enhance the accuracy of the measurement.
Similarly, for the water content (%) (F) of the gel type ion exchange resin after water content reduction, measure 5 g or more of the resin to be measured, and dry the weighed resin with a thermostatic dryer at 105 ° C for 16 hours , “((Weight of gel type ion exchange resin after reduction of water content-weight of gel type ion exchange resin in a dry state) / weight of gel type ion exchange resin after reduction of water content) × 100” .
Also, for the water content (%) (H) of the gel-type ion exchange resin before the water content reduction, weigh 5 g or more of the resin to be measured, and use the thermostated dryer at 105 ° C for 16 hours According to the formula of “((weight of gel type ion exchange resin before water content reduction-weight of gel type ion exchange resin in dry state) / weight of gel type ion exchange resin before water content reduction) × 100” Desired.

  In the ion exchange resin filling step according to the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, a gel type ion exchange resin in a water wet state is filled in a cartridge container, and the gel type ion exchange resin before water content reduction Is a step of obtaining an ion exchange resin filled cartridge filled with

  The material of the cartridge container and the cartridge container related to the ion exchange resin filling step of the method of purifying non-aqueous liquid material of the second aspect of the present invention is the ion exchange of the method of purifying non-aqueous liquid material of the first aspect of the present invention It is the same as the material of the cartridge container and the cartridge container related to the resin filling process.

  In the ion exchange resin filling step of the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the gel type ion exchange resin filled in the cartridge container is a gel type ion exchange resin in a water wet state. In the ion exchange resin filling step, the water content (H) of the gel type ion exchange resin in a water wet state filled in the cartridge container, ie, the gel type ion exchange resin before the water content reduction, is preferably gel type ion exchange The water content (G) of the resin in a saturated equilibrium state is preferably 95.0 to 100%, particularly preferably 98.0 to 100%. Usually, the water content of industrially manufactured gel type ion exchange resin is 95.0 to 100% of the water content (G) of the saturated equilibrium state of gel type ion exchange resin, and commercially available gel The moisture content of the type ion exchange resin is 95.0 to 100% of the moisture content (G) in the saturated equilibrium state of the gel type ion exchange resin. Therefore, in the ion exchange resin filling step, industrially manufactured gel type ion exchange resin in a water wet state, or commercially available gel type ion exchange resin in a water wet state is preferably used. “The moisture content (H) of the gel-type ion exchange resin in the water-wet state is preferably 95.0 to 100% of the moisture content (G) in the saturated equilibrium state of the gel-type ion exchange resin, particularly preferably “The water content of the gel-type ion exchange resin in the water-wet state in which water is actually filled in the ion exchange resin-filling step, that is, the water content of the gel-type ion exchange resin before the water content reduction is (H) / "water content in saturated equilibrium state of gel-type ion exchange resin (G)" × 100, preferably 99.0 to 100%, particularly preferably 98.0 to 100% Points to be.

  In the ion exchange resin filling step of the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the method for filling the gel container with water-wet gel type ion exchange resin in the cartridge container is not particularly limited. A method in which no foreign matter is mixed is appropriately selected.

  In the ion exchange resin-filled cartridge obtained by performing the ion exchange resin-packing step of the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, a cartridge container is filled with a gel type ion exchange resin in a water-wet state. Ion exchange resin filled cartridge. Since the ion exchange resin filled cartridge obtained by performing the ion exchange resin filling process is an ion exchange resin filled cartridge before the water content reduction process, the ion exchange resin filled process obtained by performing the ion exchange resin filling process The cartridge is, in other words, an ion exchange resin-filled cartridge in which the cartridge container is filled with the gel-type ion exchange resin before the water content reduction.

  In the water content reduction step according to the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the water content (F) of the gel type ion exchange resin after the water content reduction is the saturated equilibrium state of the gel type ion exchange resin The water content of the ion exchange resin in the cartridge container is reduced to 10.0 to 65.0%, preferably 15.0 to 25.0%, of the water content (G). “The water content (F) of the gel type ion exchange resin after reduction of water content is 10.0 to 65.0% of the water content (G) in the saturated equilibrium state of the gel type ion exchange resin, preferably 15. “To 0 to 25.0%” means “(water content of gel type ion exchange resin after water content reduction in water content reduction step (F)” / “water content of saturated equilibrium state of gel type ion exchange resin The ratio (G) ") refers to the percentage calculated by 100 until 10.0 to 65.0%, preferably 15.0 to 25.0%.

  In the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the inert gas is passed through the inside of the cartridge container, and the gel type ion exchange resin in the cartridge container is brought into contact with the inert gas. A rate reduction step (hereinafter, such a form is also described as a water content reduction step (B1)) can be performed.

  Nitrogen gas, helium gas, argon gas etc. are mentioned as an inert gas which concerns on a moisture content reduction process (B1). The purity of the inert gas is preferably as high as possible, but it may be 99.9% by volume or more. The dew point of the inert gas is preferably −50 ° C. or less, particularly preferably −60 ° C. or less.

  In the water content reduction step (B1), when the ion exchange resin filled in the cartridge container is only a cation exchange resin, the temperature of the inert gas at the time of supplying the inert gas into the cartridge container is preferably 0. It is -120 ° C, particularly preferably 60-110 ° C. In the water content reduction step (B1), when the ion exchange resin filled in the cartridge container is only an anion exchange resin or a combination of a cation exchange resin and an anion exchange resin, an inert gas is contained in the cartridge container. The temperature of the inert gas when fed is preferably 0 to 60 ° C., particularly preferably 30 to 50 ° C.

  In the water content reduction step (B1), when the inert gas comes in contact with the gel type ion exchange resin in the water wet state, the water in the gel type ion exchange resin in the water wet state is evaporated and transferred to the inert gas Thus, the water content of the gel type ion exchange resin in the water wet state is reduced. At this time, evaporation of water proceeds from the water present on and near the surface of the gel type ion exchange resin in a water wet state toward the inside.

  In the water content reduction step (B1), the water content (F) of the gel type ion exchange resin after the water content reduction is 10 of the water content (G) of the saturated equilibrium state of the macroporous or porous ion exchange resin. The contact of the inert gas with the water-wet gel-type ion exchange resin is continued until the water content becomes from 0.5 to 65.0%, preferably from 15.0 to 25.0%, and the water-wet gel-type ion exchange resin Is converted to a gel-type ion exchange resin after water content reduction, which is a predetermined water content.

  In the water content reduction step (B1), the method of causing the inert gas to pass through the cartridge container and bringing the gel type ion exchange resin in the cartridge container into contact with the inert gas is not particularly limited. Any method may be used as long as the inert gas is supplied from the one end side into the cartridge container and the inert gas is discharged from the cartridge container from the other end side of the cartridge container.

  In the water content reduction step (B1), the inert gas containing the water in the macroporous or porous ion exchange resin is treated with the inert gas dehydrator to obtain the water content in the inert gas. It can be reduced and used again as an inert gas supplied into the cartridge container in the water content reduction step (B1).

  In the method for purifying a non-aqueous liquid material according to the second aspect of the present invention, the inside of the cartridge container is depressurized and the gel type ion exchange resin is dried under reduced pressure to reduce the water content (hereinafter such a form The water content reduction step (also described as (B2)) can be performed.

  In the water content reduction step (B2), the absolute pressure at the time of drying under reduced pressure is preferably -0.05 MPa or less. In the water content reduction step (B2), when the ion exchange resin filled in the cartridge container is only a cation exchange resin, the temperature for drying under reduced pressure is preferably 0 to 120 ° C., particularly preferably 60 to 60 ° C. It is 110 ° C. In the water content reduction step (B2), when the ion exchange resin filled in the cartridge container is only an anion exchange resin or a combination of a cation exchange resin and an anion exchange resin, the temperature when drying under reduced pressure is It is preferably 0 to 60 ° C, particularly preferably 30 to 50 ° C. A well-known vacuum dryer may be used to place the resin to be treated under the above-described heating and reduced pressure drying conditions.

  In the water content reduction step (B2), the gelled ion exchange resin in the water wet state is dried under reduced pressure to evaporate the water of the gel type ion exchange resin in the water wet state, and the gel type ion exchange resin in the water wet state Moisture content is reduced. At this time, evaporation of water proceeds from the water present on and near the surface of the gel type ion exchange resin in a water wet state toward the inside.

  And, in the water content reduction step (B2), the water content (F) of the gel type ion exchange resin after the water content reduction is 10.0 to 65 of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin. The gel-type ion exchange resin in the water-wet state is dried under reduced pressure until the water content becomes 0.1%, preferably 15.0-25.0%, and the gel-type ion exchange resin in the water-wet state has a predetermined moisture content It is converted to a gel-type ion exchange resin after water content reduction.

  In the water content reduction step (B2), a method for drying the gel type ion exchange resin in a water wet state under reduced pressure is not particularly limited. For example, the ion exchange resin filled cartridge is allowed to stand in a reduced pressure drying device and dried under reduced pressure. There is a method in which the inside of the apparatus is depressurized, or the inside of a depressurized drying apparatus is depressurized and heated while being dried under reduced pressure. When the inside of the reduced-pressure drying apparatus is returned to normal pressure after drying under reduced pressure, it is preferable that the pressure be reduced to normal pressure by introducing an inert gas of high purity into the pressure reducing apparatus so that impurities in the atmosphere do not mix. .

  Further, in the method for purifying a non-aqueous liquid substance of the present invention, the water content reduction step (hereinafter referred to as “water content reduction step” is carried out by heating the ion exchange resin filled cartridge filled with gel type ion exchange resin in a heating device of inert gas atmosphere. Such a form can be performed also as a moisture content reduction process (B3).

  In the water content reduction step (B3), when the ion exchange resin with which the cartridge container is filled is only a cation exchange resin, the heating temperature when heating the ion exchange resin filled cartridge is preferably 0 to 120 ° C., particularly Preferably it is 60-110 degreeC. In the water content reduction step (B3), the ion exchange resin filled in the cartridge container is only an anion exchange resin or a combination of a cation exchange resin and an anion exchange resin, the ion exchange resin filled cartridge is heated. The heating temperature is preferably 0 to 60 ° C., particularly preferably 30 to 50 ° C.

  In the water content reduction step (B3), by heating the gel type ion exchange resin in the water wet state, the water of the gel type ion exchange resin in the water wet state is evaporated and the gel type ion exchange resin in the water wet state is Moisture content is reduced. At this time, evaporation of water proceeds from the water present on and near the surface of the gel type ion exchange resin in a water wet state toward the inside.

  And, in the water content reduction step (B3), the water content (F) of the gel type ion exchange resin after the water content reduction is 10.0 to 65 of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin. The gel-type ion exchange resin in the water-wet state is heated until the water content becomes 0. 0%, preferably 15.0 to 25.0%, and the gel-type ion exchange resin in the water-wet state has a predetermined moisture content It is converted to gel type ion exchange resin after rate reduction.

  In the water content reduction step (B3), the method for heating the gel type ion exchange resin in a water wet state is not particularly limited, and heating the ion exchange resin filled cartridge in a heating device under an inert gas atmosphere Any method can be used.

  Thus, by performing the water content reduction step according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention, a gel type ion exchange resin in a water wet state (gel type ion exchange before water content reduction) Resin) is converted to a gel type ion exchange resin (gel type ion exchange resin after water content reduction) whose water content is a predetermined value, and the cartridge container is filled with the gel type ion exchange resin after water content reduction. An ion exchange resin filled cartridge is obtained. And, in the water content reduction step, the water content (F) of the gel type ion exchange resin after the water content reduction is the degree of water content reduction, and the water content (G) of the saturated equilibrium state of the gel type ion exchange resin. By setting the content to 10.0 to 65.0%, preferably 15.0 to 25.0%, the water content can be obtained by a simple method such as the water content reduction step (B2) or the water content reduction step (B3) Can be reduced, and the amount of the initial blow waste solution can be reduced. On the other hand, if the water content (F) of the gel type ion exchange resin after reduction of the water content relative to the water content (G) in the saturated equilibrium state of the gel type ion exchange resin exceeds the above range, the amount of the initial blow waste solution becomes large. It will If the water content (F) of the macroporous or porous ion exchange resin after reduction of the water content relative to the water content (G) in the saturated equilibrium state of the gel type ion exchange resin is less than the above range, Although the amount is reduced, the cost for reducing the water content of the gel type ion exchange resin is increased.

  In the initial blowing step according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention, the unrefined non-aqueous liquid material is contained in a cartridge container filled with a gel type ion exchange resin after water content reduction. It is a step of passing the solution and discharging the initial blow waste solution from the inside of the cartridge container.

  The initial blowing step according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention is a pretreatment step performed before purifying the non-aqueous liquid material, mainly containing water contained in the gel type ion exchange resin. It is carried out for the purpose of reducing the water content by substituting the non-aqueous liquid substance and reducing the water eluting from the gel type ion exchange resin to the non-aqueous liquid substance so as to enable normal purification.

  Then, in the initial blowing step according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention, the gel type ion exchange resin after water content reduction is filled until the ion exchange filling cartridge is in a predetermined state. Continue to pass unrefined non-aqueous liquid material into the cartridge container. At this time, an initial blow waste solution is generated.

  In the purification process according to the purification method of the non-aqueous liquid material of the second aspect of the present invention, the unrefined non-aqueous liquid material is passed through the cartridge container of the ion exchange resin-filled cartridge subjected to the initial blowing step. Thus, the gel non-aqueous liquid substance is brought into contact with the gel type ion exchange resin in the cartridge container to purify the non-aqueous liquid substance, thereby obtaining a purified non-aqueous liquid substance.

  Then, by performing the purification step according to the method for purifying a non-aqueous liquid material of the second aspect of the present invention, a high-purity non-aqueous liquid material from which impurities have been removed can be obtained.

  The present inventors (1) contact with a non-aqueous liquid material at the time of initial blow, and a large amount of water flowing out from the ion exchange resin is ions in the pores of the surface and inside of the gel type ion exchange resin. Since the gel type ion exchange resin has a smaller specific surface area and pore volume than the macroporous or porous ion exchange resin, it is water which exists as free water molecules which are not in a hydrated state with the exchange group. Water molecules present in the pores and in a hydrated state with the ion exchange group hardly leak out from the ion exchange resin even when in contact with the non-aqueous liquid substance, (2) an inert gas is continuously added to the ion exchange resin When reducing the water content of the ion exchange resin in a water-wet state by contacting, drying the ion exchange resin under reduced pressure, heating the ion exchange resin, etc. In the exchange resin, the water content (A) of the ion exchange resin after reduction of water content is 10.0 to 97.0%, preferably 10.0% or more of the water content (B) of the saturated equilibrium state of the ion exchange resin By reducing the water content to 90.0% or less, in the gel type ion exchange resin, the water content (F) of the ion exchange resin after the water content reduction is the saturation equilibrium state of the ion exchange resin Effluence from the ion exchange resin during initial blow by reducing the water content to 10.0 to 65.0%, preferably 15.0 to 25.0% of the water content (G) of As it is possible to reduce free water molecules that are not in a hydrated state with ion exchange groups on the easy surface and internal pores, the amount of water outflow to the initial blow waste solution decreases, (3) these Reduce the amount of initial blowout We have found that it is possible.

  On the other hand, in order to eliminate the influence of moisture in the ion exchange resin at the time of initial blow, it is conceivable to dry the ion exchange resin before filling the cartridge container, but the ion exchange resin after the drying step and the drying In the process of transferring into the cartridge, contact with metal or contact with the atmosphere containing metal or fine particles causes contamination of the ion exchange resin.

  In the purification method of the non-aqueous liquid substance of the present invention, as in the embodiment shown in FIGS. 1 to 4, after the ion exchange resin filling step and the water content reduction step are performed, the ion exchange resin filled cartridge is Inside the metal removal column, feed the unrefined non-aqueous liquid material into the metal removal column, pass through the storage container of the metal removal column, and pass through the unrefined non-water liquid material into the cartridge container of the ion exchange resin filled cartridge. Although the solution is passed through to carry out the initial blowing step and the purification step, the present invention is not limited thereto. As a form of the purification method of the non-aqueous liquid substance of the present invention, after performing the ion exchange resin filling step and the water content reduction step, the ion exchange resin filled cartridge is installed in the metal removal column, and the metal removal column is The unrefined non-aqueous liquid material is supplied, passed through the storage container of the metal removal column, and passed through the unrefined non-aqueous liquid material into the cartridge container of the ion exchange resin-filled cartridge to carry out the initial blowing step and purification The form which performs a process is mentioned. Further, as another embodiment of the method for purifying a non-aqueous liquid substance of the present invention, after performing the ion exchange resin filling step and the water content reduction step, unrefined directly in the cartridge container of the ion exchange resin filled cartridge. There is a mode in which the non-aqueous liquid substance is passed to carry out the initial blowing step and the purifying step. In other words, another embodiment of the method for purifying non-aqueous liquid material of the present invention supplies unrefined non-aqueous liquid material directly into the cartridge container of an ion exchange resin-filled cartridge without using a metal removal column. It is a form.

  Among the purification methods of the non-aqueous liquid material of the present invention, after performing the ion exchange resin filling step and the water content reduction step, the unrefined non-aqueous liquid material is directly passed into the cartridge container of the ion exchange resin filled cartridge. As an ion exchange resin filled cartridge used for the form which carries out liquid and performs an initial stage blow process and a refinement process, ion exchange resin cartridge 120 shown in Drawing 5 is mentioned, for example. The ion exchange resin cartridge 120 has a cylindrical portion 2 filled with granular ion exchange resin 1a in a water wet state, and a passing hole 7 for the liquid to be treated (unrefined non-aqueous liquid substance). An upper lid 103 provided at the upper end of the cylindrical portion 2 provided with a connecting portion 102 screwed to the end of the infusion tube of the liquid to be treated (unrefined non-aqueous liquid substance); A through hole 8 for the liquid substance is formed, and it is connected to the lower lid 4 provided at the lower end of the cylindrical portion 2 and the lower lid, and screwed into the end of the treatment liquid (non-aqueous liquid substance after purification) And a particulate ion exchange resin 1 a filled in the interior of the cylindrical portion 2. In the embodiment shown in FIG. 5, the lower lid 4 and the treatment liquid discharge pipe 105 are integrally formed. Further, in the embodiment shown in FIG. 5, the lower lid 4 to which the cylindrical portion 2, the upper lid 3 and the treatment liquid discharge pipe 105 are attached is a cartridge container. Further, the upper end side tube diameter reduction portion 11 is formed on the upper end side inside the cylindrical portion 2, and the lower end side tube diameter reduction portion 12 is formed on the lower end side inside the cylindrical portion 2 There is. Then, in order to prevent the ion exchange resin 1 from flowing out from the cylindrical portion 2, the mesh 9 is provided between the upper end side tube diameter reduction portion 11 and the upper lid 3 at the upper end of the filling region of the ion exchange resin. The mesh 10 is attached at the lower end of the ion exchange resin-filled area by being sandwiched between the lower end side tube diameter reduced portion 12 and the upper lid 4 by being pinched by the outer edge. It is done. In addition, the mesh 9 and the mesh 10 have a clearance of the magnitude | size of the extent which permeate | transmits a to-be-processed liquid and does not permeate | transmit granular ion exchange resin 1a.

  In the method for purifying non-aqueous liquid material according to the present invention, as in the embodiment shown in FIGS. 1 to 4, after the ion exchange resin filling step and the water content reduction step are performed, the ion exchange resin filled cartridge is Although the initial blowing step and the purification step are performed after being installed in the removal column, when the water content reduction step (A1) is adopted as the water content reduction step, it is not limited to this. Among the purification methods of the non-aqueous liquid material of the present invention, as an embodiment in which the water content reduction step (A1) is adopted as the water content reduction step, the ion exchange resin filling step and the water content reduction step are carried out. There is a mode in which the resin-filled cartridge is installed in the metal removal column, and then the initial blowing step and the purification step are performed. Among the methods for purifying the non-aqueous liquid material of the present invention, as another embodiment employing the water content reduction step (A1) as the water content reduction step, after performing the ion exchange resin filling step, the ion exchange resin filled cartridge Is placed in a metal removal column, and an inert gas is introduced from an inert gas introduction tube provided at an appropriate position such as a metal removal column, an infusion tube of a liquid to be treated, and the like. The water content reduction step (A1) is performed by discharging the inert gas from an inert gas discharge pipe provided at an appropriate position such as an infusion pipe of the treatment liquid, and then an initial blowing step and a purification step Can be mentioned.

The ion exchange resin-filled cartridge with the open air blocking member according to the first aspect of the present invention comprises a cartridge container;
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A macroporous or porous ion exchange resin filled in the cartridge container, wherein the water content (D) is 10.0 to 97.0% of the water content (E) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an outside air blocking member, characterized in that

  The cartridge container according to the ion exchange resin-filled cartridge with the external air blocking member of the first aspect of the present invention is the same as the cartridge container according to the method of purifying a non-aqueous liquid substance of the first aspect of the present invention. The macroporous or porous ion exchange resin according to the first embodiment of the ion exchange resin-filled cartridge with open air blocking member of the first aspect of the present invention is a macro according to the purification method of the non-aqueous liquid substance of the first aspect of the present invention. It is the same as the porous or porous ion exchange resin.

  In the ion exchange resin-filled cartridge having the open air blocking member according to the first aspect of the present invention, the macroporous or porous ion exchange resin packed in the cartridge container has a moisture content (D) of which the water content is in a saturated equilibrium state. It is a macroporous or porous ion exchange resin having a percentage (E) of 10.0 to 97.0%, preferably 10.0% to less than 90.0%. “10. The water content (D) of the macroporous or porous ion exchange resin filled in the cartridge container is the water content (E) of the saturated equilibrium water content (E) of the macroporous or porous ion exchange resin. “0 to 97.0%, preferably 10.0% or more and less than 90.0%” means “(water content of macroporous or porous ion exchange resin filled in cartridge container (D)” / “The moisture content (E) in saturated equilibrium state of macroporous or porous ion exchange resin” × 100, the percentage calculated is 10.0 to 97.0%, preferably 10.0% to 90.0. Indicates that it is less than%.

  The outside air blocking member according to the ion exchange resin-filled cartridge with the outside air blocking member of the first embodiment of the present invention is a member for blocking the air flow between the inside of the cartridge and the outside air.

  Examples of the outside air blocking member according to the ion exchange resin-filled cartridge with the outside air blocking member of the first embodiment of the present invention include, for example, the embodiment shown in FIG. In FIG. 6, in the ion exchange resin-filled cartridge 40 with the external air blocking member, on the upper end side of the cylindrical portion of the ion exchange resin-filled cartridge 20a, the passage hole of the treatment liquid formed in the upper lid of the cylindrical portion is completely covered. The upper cap member 33a is attached, and at the lower end side of the cylindrical portion of the ion exchange resin-filled cartridge 20a, the passage hole of the processing liquid formed in the lower lid of the cylindrical portion and the opening of the insertion tube are completely The lower cap member 33b is attached so as to cover it. The space between the upper cap member 33a and the cylindrical portion and the space between the lower cap member 33b and the cylindrical portion are sealed to the extent that outside air does not enter the cartridge container.

  The material of the cap member is not particularly limited. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), low density polyethylene And high density polyethylene.

  A member may be attached to the inside of the upper cap member 33a and the lower cap member 33b in order to improve the sealing performance of an O-ring, a seal tape, and the like.

  As another embodiment of the outside air blocking member according to the ion exchange resin cartridge with the outside air blocking member of the first embodiment of the present invention, for example, the whole of the ion exchange resin filled cartridge is wrapped and air flow between the inside and outside air is blocked. Surrounding bags. The material of the surrounding bag is a material that does not transmit air.

  In the ion exchange resin-filled cartridge having the open air blocking member according to the first aspect of the present invention, the water content (D) of the macroporous or porous ion exchange resin packed in the cartridge container is the water content in the saturated equilibrium state Since it is 10.0 to 97.0% of (E), preferably 10.0% or more and less than 90.0%, in other words, water that easily flows out of the ion exchange resin during initial blowing decreases Since the present macroporous or porous ion exchange resin is filled in the cartridge container, the initial blowing step and the purification step are carried out using the ion exchange resin-filled cartridge with the open air blocking member of the first embodiment of the present invention. If done, the initial blow waste can be reduced.

According to a second aspect of the present invention, there is provided an ion exchange resin-filled cartridge having an open air blocking member according to the second aspect of the present invention, comprising
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A gel type ion exchange resin filled in the cartridge container and having a water content (I) of 10.0 to 65.0% of a water content (J) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an outside air blocking member, characterized in that

  The cartridge container according to the ion exchange resin-filled cartridge according to the second aspect of the present invention is the same as the cartridge container according to the method for purifying a non-aqueous liquid substance according to the second aspect of the present invention. In addition, the gel type ion exchange resin according to the ion exchange resin-filled cartridge according to the second aspect of the present invention is a gel type ion exchange resin according to the second aspect of the present invention. It is the same as the exchange resin.

  In the ion exchange resin-filled cartridge according to the second aspect of the present invention, the gel-type ion exchange resin packed in the cartridge container has a water content (I) of which the water content in saturated equilibrium (I) The gel type ion exchange resin is 10.0 to 65.0%, preferably 15.0 to 25.0%. "The water content (I) of the gel type ion exchange resin filled in the cartridge container is 10.0 to 65. of the water content (J) of the saturated equilibrium state of the macroporous or porous ion exchange resin. 0%, preferably 15.0 to 25.0%, “(water content of gel type ion exchange resin filled in cartridge container (I)) /” macroporous or porous ion exchange resin The percentage calculated by water content in saturated equilibrium state (J) ") x 100 is 10.0 to 65.0%, preferably 15.0 to 25.0%.

  The outside air blocking member according to the ion exchange resin-filled cartridge with the outside air blocking member according to the second embodiment of the present invention is the same as the outside air blocking member according to the ion exchange resin filled cartridge with the outside air blocking member according to the first embodiment of the present invention. is there.

  According to the ion exchange resin-filled cartridge having the open air blocking member of the second aspect of the present invention, the water content (I) of the gel type ion exchange resin packed in the cartridge container is the water content (J) of the saturated equilibrium state. Since it is 10.0 to 65.0%, preferably 15.0 to 25.0%, in other words, a gel type ion exchange resin in which water easy to flow out from the ion exchange resin at the time of initial blow is reduced However, since the cartridge container is filled with the ion exchange resin-filled cartridge according to the present invention, the initial blow waste solution can be reduced if the initial blow step and the purification step are performed.

  Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.

Example 1
・ Reduction test of water content <ion exchange resin filling process>
The ion exchange resin A (water content 60.8%) in a saturated equilibrium state by bringing the following ion exchange resin A (macroporous type or porous type) into contact with air at 25 ° C. and 100% relative humidity for 30 minutes or more I got
Next, as the ion exchange resin, the cation exchange resin A in a saturated equilibrium state was filled in the cartridge container, and an ion exchange resin-filled cartridge B1 shown in FIG. 1 was produced. Details of the loaded ion exchange resin and O-ring are shown below, and details of the cartridge container are shown in Table 1.
<Water content reduction process>
Next, nitrogen gas (purity 99.99% or more) at 25 ° C is supplied to the ion exchange resin-filled cartridge B1 at a flow rate of 60 L / hour for 75 minutes, and nitrogen gas is supplied to the ion exchange resin-filled cartridge B1. The water content of the ion exchange resin was reduced by passing it to obtain an ion exchange resin-filled cartridge C1 filled with the ion exchange resin after the water content reduction.
<Calculation of reduction rate of water content>
Then, the supply of nitrogen gas was stopped, the ion exchange resin in the ion exchange resin-filled cartridge C1 was taken out, and the water content was measured. As a result, the water content was 58.0%. From these, the water content of the macroporous or porous ion exchange resin after reduction of water content (A) is 95.4% of the water content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin Calculated.

Initial Blow Test In the same manner as described above, the ion exchange resin filling step and the water content reduction step were performed to produce an ion exchange resin filled cartridge C1.
<Initial blow process>
The ion exchange resin-filled cartridge C1 was placed in a PFA housing for demetallization filter manufactured by Pall Corporation, and a metal removal column was assembled.
Subsequently, isopropyl alcohol (SE grade, water content 50 mass ppm or less) is supplied to the metal removal column as a liquid to be treated, SV-4 = resin volume (ml) × 4 · h ⁻¹ , and bed volume (BV) The supply of isopropyl alcohol to the liquid to be treated was continued until 30), and an initial blowing step was performed. The change in the amount of water in the initial blow waste solution generated during the initial blow step was measured. As a result, the water content at BV = 10.5 was 800 mass ppm, and the water content at BV = 14 was 400 ppm. Further, the change in the water content in the initial blow waste solution is shown in FIG.
<Purification process>
Supply of isopropyl alcohol of the liquid to be treated to the metal removal column was continued, and isopropyl alcohol of the treatment liquid at a bed volume (BV) of 16.1 was collected, and the water content was measured. As a result, the water content of isopropyl alcohol in the treatment liquid was 300 ppm.

(Example 2)
In the water content reduction step, the water content (A) of the macroporous or porous ion exchange resin after reduction of the water content is the water content (B) of the saturated equilibrium state water content (B) of the macroporous or porous ion exchange resin. The same procedure as in Example 1 was carried out except that the water content was reduced to 5%.
As a result, in the initial blowing step, the water content at BV = 10.7 was 800 mass ppm, and the water content at BV = 13.0 was 400 mass ppm. Further, the change in the water content in the initial blow waste solution is shown in FIG.
In addition, in the purification step, the moisture content of isopropyl alcohol of the treatment liquid at a point when the bed volume (BV) was 14.1 was 300 ppm.

(Example 3)
・ Reduction test of water content <ion exchange resin filling process>
The following ion exchange resin B (gel type) was brought into contact with air at 25 ° C. and 100% relative humidity for 30 minutes or more to obtain ion exchange resin B in a saturated equilibrium state (water content 56.4%).
Next, as the ion exchange resin, the cation exchange resin B in a saturated equilibrium state was filled in the cartridge container, and an ion exchange resin-filled cartridge B2 shown in FIG. 1 was produced. Details of the loaded ion exchange resin and O-ring are shown below, and details of the cartridge container are shown in Table 1.
<Water content reduction process>
Next, the ion exchange resin-filled cartridge B2 is allowed to stand in a vacuum dryer, and then dried under reduced pressure at 40 ° C. for 21 hours at 40 ° C. under a pressure of 0 kPa to reduce the water content of the ion exchange resin. An ion exchange resin-filled cartridge C2 filled with ion exchange resin was obtained.
<Calculation of reduction rate of water content>
The ion exchange resin in the ion exchange resin-filled cartridge C2 was taken out, and the water content was measured. As a result, the water content was 13.8%. From these, the water content (F) of the gel type ion exchange resin after the water content reduction was calculated to be 24.5% of the water content (G) in the saturated equilibrium state of the gel type ion exchange resin.

Initial Blow Test In the same manner as described above, the ion exchange resin filling step and the water content reduction step were performed to produce an ion exchange resin filled cartridge C2.
<Initial blow process>
The ion exchange resin-filled cartridge C2 was placed in a PFA housing for demetallization filter manufactured by Pall Corporation, and the metal removal column was assembled.
Subsequently, isopropyl alcohol (SE grade, water content 50 mass ppm or less) is supplied to the metal removal column as a liquid to be treated, SV-4 = resin volume (ml) × 4 · h ⁻¹ , and bed volume (BV) The supply of isopropyl alcohol to the liquid to be treated was continued until 30), and an initial blowing step was performed. The change in the amount of water in the initial blow waste solution generated during the initial blow step was measured. As a result, the water content at BV = 14.9 was 800 mass ppm, and the water content at BV = 20.0 was 400 mass ppm. Further, the change of the water content in the initial blow waste solution is shown in FIG.
<Purification process>
Supply of isopropyl alcohol of the liquid to be treated to the metal removal column was continued, and isopropyl alcohol of the treatment liquid at a bed volume (BV) of 22.6 was collected, and the water content was measured. As a result, the water content of isopropyl alcohol in the treatment liquid was 300 ppm.

(Example 4)
In the water content reduction step, the water content is decreased until the water content (F) of the gel type ion exchange resin after the water content reduction becomes 12.9% of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin. It carried out like Example 3 except making it reduce.
As a result, in the initial blowing step, the water content at BV = 8.2 was 800 mass ppm, and the water content at BV = 9.6 was 400 mass ppm. Further, the change of the water content in the initial blow waste solution is shown in FIG. Further, in the purification step, the moisture content of isopropyl alcohol of the treatment liquid was 300 ppm when the bed volume (BV) was 15.0.

<Ion exchange resin>
-Ion exchange resin A: A mixture of macroporous or porous strong acid cation exchange resin and macroporous or porous strong base anion exchange resin, manufactured by Organo Corporation (Olllight DS-7), Material: styrene-divinylbenzene copolymer, type of ion exchange group: sulfonic acid group, trimethyl ammonium group, cation exchange equivalent: 1.7 mg equivalent / ml wet resin, anion exchange equivalent: 0.8 mg equivalent / ml wet resin, Average particle size in dry state: 80 to 400 μm, moisture content at saturated equilibrium state 60.8% by mass.
-Ion exchange resin B: gel type strongly basic anion exchange resin, manufactured by Organo Corporation (Orlite DS-3), resin material: styrene-divinylbenzene copolymer, type of ion exchange group: sulfonic acid group Trimethylammonium group, cation exchange equivalent: 2.1 mg equivalent / ml wet resin, anion exchange equivalent: 1.0 mg equivalent / ml wet resin, dry average particle size: 80 to 400 μm, saturated equilibrium water content 56. 4 mass%.
<O ring>
Product name: PFA coated O-ring, material: Viton coated with PFA, wire diameter: 3.53 ± 0.10 mm, inner diameter: 37.69 ± 0.38 mm, outer diameter: 44.75 mm

<Measurement of moisture content>
The ion exchange resin is brought into contact with the atmosphere at 25 ° C. and an relative humidity of 100% for 30 minutes or more to saturate the ion exchange resin to obtain the ion exchange resin in a saturated equilibrium state. Further, the ion exchange resin in a saturated equilibrium state was dried at 105 ° C. for 16 hours in a thermostatic dryer to obtain a dry ion exchange resin. Then, the moisture content (%) (B) of the macroporous or porous ion exchange resin in the saturated equilibrium state can be expressed as “((weight of the macroporous or porous ion exchange resin in the saturated equilibrium state before drying-dry state Of the macroporous or porous ion exchange resin) / the weight of the macroporous or porous ion exchange resin in a saturated equilibrium state before drying) × 100 ”. In addition, the water content (%) (G) of the gel type ion exchange resin in the saturated equilibrium state can be expressed as “((weight of gel type ion exchange resin in saturated equilibrium state before drying-weight of gel type ion exchange resin in dry state ) / Weight of macroporous or porous ion exchange resin in a saturated equilibrium state before drying) × 100 ". In order to enhance the accuracy of the measurement, 5 g or more of ion exchange resin in a saturated equilibrium state before drying was collected.

(Comparative example 1)
In the same manner as in Example 1, the ion exchange resin filling step was performed to produce an ion exchange resin filled cartridge B1.
Next, the ion exchange resin-filled cartridge B1 was installed in a PFA housing for demetallization filter manufactured by Pall Corporation, and the metal removal column was assembled.
Subsequently, isopropyl alcohol (SE grade, water content 50 mass ppm or less) is supplied to the metal removal column as a liquid to be treated, SV-4 = resin volume (ml) × 4 · h ⁻¹ , and bed volume (BV) The supply of isopropyl alcohol to the liquid to be treated was continued until 30), and an initial blowing step was performed. The change in the amount of water in the initial blow waste solution generated during the initial blow step was measured. As a result, the water content at BV = 12.5 was 800 mass ppm, and the water content at BV = 16 was 400 mass ppm. Further, the change in the water content in the initial blow waste solution is shown in FIG.
That is, in Comparative Example 1, an initial blow test was performed using an ion exchange resin not subjected to the water content reduction step.

(Comparative example 2)
In the same manner as in Example 3, the ion exchange resin filling step was performed to produce an ion exchange resin filled cartridge B2.
Next, the ion exchange resin-filled cartridge B2 was installed in a PFA housing for demetallization filter manufactured by Pall Corporation, and the metal removal column was assembled.
Subsequently, isopropyl alcohol (SE grade, water content 50 mass ppm or less) is supplied to the metal removal column as a liquid to be treated, SV-4 = resin volume (ml) × 4 · h ⁻¹ , and bed volume (BV) The supply of isopropyl alcohol to the liquid to be treated was continued until 30), and an initial blowing step was performed. The change in the amount of water in the initial blow waste solution generated during the initial blow step was measured. As a result, the water content at BV = 15.6 was 800 mass ppm, and the water content at BV = 20.8 was 400 mass ppm. Further, the change of the water content in the initial blow waste solution is shown in FIG.
That is, in Comparative Example 2, an initial blow test was performed using an ion exchange resin not subjected to the water content reduction step.

(Example 5)
In the same manner as in Example 3, the ion exchange resin filling step was performed to produce an ion exchange resin filled cartridge B2.
<Water content reduction process>
Next, the ion exchange resin-filled cartridge B2 is allowed to stand in a vacuum dryer, and then dried under reduced pressure for 21 hours at 40 ° C. under a gauge pressure of 0 kPa to reduce the water content of the ion exchange resin and reduce the water content The ion exchange resin filled cartridge C3 filled with the later ion exchange resin was obtained.
<Calculation of reduction rate of water content>
Then, the supply of nitrogen gas was stopped, the ion exchange resin in the ion exchange resin-filled cartridge C3 was taken out, and the water content was measured. As a result, the water content was 36.3%. From these, the water content (F) of the gel type ion exchange resin after the water content reduction was calculated to be 64.4% of the water content (G) in the saturated equilibrium state of the gel type ion exchange resin.

<Initial blow test>
In the same manner as described above, the ion exchange resin filling step and the water content reduction step were performed to produce an ion exchange resin filled cartridge C3.
Next, the ion exchange resin-filled cartridge C3 was installed in a PFA housing for demetallization filter manufactured by Pall Corporation, and the metal removal column was assembled.
Subsequently, isopropyl alcohol (SE grade, water content 50 mass ppm or less) is supplied to the metal removal column as a liquid to be treated, SV-4 = resin volume (ml) × 4 · h ⁻¹ , and bed volume (BV) The supply of isopropyl alcohol to the liquid to be treated was continued until 30), and an initial blowing step was performed. The change in the amount of water in the initial blow waste solution generated during the initial blow step was measured. As a result, the water content at BV = 14.6 was 800 mass ppm, and the water content at BV = 19.1 was 400 mass ppm. Further, the change of the water content in the initial blow waste solution is shown in FIG.

1a Granular macroporous or porous ion exchange resin in water wet state or granular gel type ion exchange resin 1b in water wet state Macroporous or porous ion exchange resin or gel type ion exchange resin 1c after water content reduction Macroporous type or porous type ion exchange resin or gel type ion exchange resin 2 tube part after initial blow 3, 103 Upper lid 4 Lower lid 5 Insertion tube 6 O ring 7 Passage hole of liquid to be treated 8 Passage hole of treatment liquid 9 Mesh DESCRIPTION OF SYMBOLS 10 mesh 11 upper end side pipe diameter reduction part 12 lower end side pipe diameter reduction parts 20a, 20b, 20c, 120 ion exchange resin filled cartridge 21 storage container 22 treated liquid supply port 23 treated liquid discharge pipe 24 inner wall 25 of treated liquid discharge pipe Infusion pipe 26 for treatment liquid Infusion pipe 27 for treatment liquid Space between cylindrical portion and storage container 28 connecting pipe 30 metal removal column 31 to be treated Solution 32 Treatment solution 33a Upper cap member 33b Lower cap member 40 Ion exchange resin filled cartridge 51 with external air blocking member Groove for O-ring attachment 102 Connection part 105 Treatment solution discharge pipe 311 Initial blow waste solution

Claims (4)

A method for purifying a non-aqueous liquid material, comprising the steps of: contacting a non-aqueous liquid material with a macroporous or porous ion exchange resin to remove impurities from the non-aqueous liquid material,
The ion exchange resin is filled with an ion exchange resin-filled cartridge in which a macroporous or porous ion exchange resin in a water wet state is filled in a cartridge container and the macroporous or porous ion exchange resin is filled before the water content reduction. Process,
The water content (A) of the macroporous or porous ion exchange resin after reduction of water content is 10.0 to 97. of the water content (B) of the saturated equilibrium state of the macroporous or porous ion exchange resin. A moisture content reducing step of reducing the moisture content of the macroporous or porous ion exchange resin in the cartridge container to 0%;
The unrefined non-aqueous liquid material is passed through the cartridge container filled with the macroporous or porous ion exchange resin after the reduction of water content, and the initial blow waste solution is discharged from the cartridge container Initial blow process,
By passing the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the macroporous or porous ion exchange resin in the cartridge container, Purifying the non-aqueous liquid material to obtain a purified non-aqueous liquid material;
A method of purifying a non-aqueous liquid substance, comprising: A method for purifying a non-aqueous liquid material, which comprises contacting a non-aqueous liquid material with a gel type ion exchange resin to remove impurities from the non-aqueous liquid material, comprising:
An ion exchange resin filling step of filling a cartridge container with a gel type ion exchange resin in a water wet state and obtaining an ion exchange resin filled cartridge filled with the gel type ion exchange resin before water content reduction;
The cartridge until the water content (F) of the gel type ion exchange resin after water content reduction becomes 10.0 to 65.0% of the water content (G) of the saturated equilibrium state of the gel type ion exchange resin A moisture content reduction step of reducing the moisture content of the gel type ion exchange resin in a container;
An initial blowing step of passing the unrefined non-aqueous liquid material into the cartridge container filled with the gel type ion exchange resin after reduction of water content and discharging an initial blow waste solution from the cartridge container; ,
By pouring the unrefined non-aqueous liquid material into the cartridge container, the unrefined non-aqueous liquid material is brought into contact with the gel-type ion exchange resin in the cartridge container to cause the non-aqueous liquid to flow. Purifying the substance to obtain the purified non-aqueous liquid substance;
A method of purifying a non-aqueous liquid substance, comprising: A cartridge container,
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A macroporous or porous ion exchange resin filled in the cartridge container, wherein the water content (D) is 10.0 to 97.0% of the water content (E) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an ambient air blocking member characterized by A cartridge container,
A supply port for supplying a non-aqueous liquid substance into the cartridge container;
An outlet for discharging the non-aqueous liquid substance from the inside of the cartridge container;
A gel type ion exchange resin filled in the cartridge container and having a water content (I) of 10.0 to 65.0% of a water content (J) in a saturated equilibrium state;
An ion exchange resin-filled cartridge having
An outside air blocking member for blocking air flow between the inside of the cartridge and the outside air;
Consisting of
An ion exchange resin-filled cartridge with an ambient air blocking member characterized by