TWI399342B - Process for the preparation of waste liquid containing tetraalkylammonium ion - Google Patents

Description

Method for treating developing waste liquid containing tetraalkylammonium ion

The present invention relates to a method for treating a developing waste liquid containing a tetraalkylammonium ion. In the case of the cation exchange resin or the chelating resin used for the treatment for regenerating the development waste liquid, when the hydrogen ion type is converted into the tetraalkylammonium ion type, the sharp swelling at the time of conversion can be suppressed. The method for treating a developing waste liquid containing tetraalkylammonium ions can be repeatedly used for long-term regeneration.

In the lithography step of the process of the electronic component such as a semiconductor device, a liquid crystal display, or a printed circuit board, tetraalkylammonium hydroxide (hereinafter abbreviated as TAAH) is used as the alkali developing solution for the photoresist. Therefore, in the developing step or the washing step of the lithography step, a photoresist mainly composed of a novolak resin or the like and a TAA ion-containing image mainly composed of tetraalkylammonium ions (hereinafter referred to as TAA ions) are discharged. Waste liquid.

At present, the above-mentioned developing waste liquid containing TAA ions is discarded by a conventional drainage treatment, but in recent years, as the production amount of semiconductors and liquid crystals is greatly increased, the consumption of the developing liquid increases. The discharge amount of the developing waste liquid containing TAA ions also increases. Therefore, in order to effectively utilize the resources, it is proposed to regenerate the TAHA ion-containing developing waste liquid by removing impurities such as organic substances or metal ions from the photoresist from the waste liquid and reusing TAAH. For example, there is a proposal to remove a metal ion or the like by electrodialysis or electrolysis of the above-mentioned developing waste liquid, and to adsorb a metal ion in the developing waste liquid by a cation exchange resin or a chelating resin. In addition, a method of purifying and recovering TAAH by electrolysis after removing the metal ion or the like in the development waste liquid by the cation exchange resin or the chelating resin is removed.

Among them, a method in which a cation exchange resin or a chelating resin adsorbs metal ions or the like in the development waste liquid is removed, and it is known that a hydrogen ion type (H-shaped) cation due to an acid is washed by ultrapure water. After exchanging the resin or the chelating resin, the TAAH having a concentration of 1 mol/L is brought into a tetraalkylammonium ion type (TAA ion type), and then the developing waste liquid containing the TAA ion is contacted to remove metal ions or the like. The method of impurities. Further, a method for regenerating the cation exchange resin or the chelating resin by contacting the developer waste liquid is to remove metal ions or the like from the cation exchange resin or the chelating resin by contact with an acid, and then convert the resin. The TAA ion type is used repeatedly (see Patent Document 1).

However, when the cation exchange resin or the chelating resin is in the TAA ion type, the water is swollen in the resin as compared with the H type. Therefore, if the H-form and the TAA ion-type conversion are repeated, the resin is Repeated shrinkage and swelling, cracking occurs, and the resin will pulverize. Therefore, when the resin is regenerated and reused, there is a problem in that a pressure difference occurs during the liquid passage due to the pulverized material of the resin, or an operation failure such as an extremely low flow rate is caused.

Further, Patent Document 2 discloses that a development waste liquid containing TAA ions is directly treated in a H-type cation exchange resin or a chelating resin, and after the TAA ions are adsorbed and treated by the resin, the TAA ion-containing TAA is dehydrated by an acid or the like. When the method of treating the ionized waste liquid is used, TAA is used as the development waste liquid. A method of treating a waste liquid having an ion concentration of 0.016 mol/L or less (0.015 mass% or less). The method is characterized in that the use of a thin TAA ion developing waste liquid suppresses the sharp swelling of the resin when converted into a TAA ion type, and effectively suppresses the cation exchange resin or the chelate when the resin is regenerated by repeated use. Deterioration of the resin. However, it is necessary to use a thin solution as a developing waste liquid, which is problematic in terms of an increase in the amount of waste liquid and the like. Further, when the developer waste liquid to be treated has a high concentration, it is necessary to have a dilution operation such as adding water, and there is also a problem that the operation becomes complicated.

[Patent Document 1] JP-A-2003-190822 (Patent Document 2) JP-A-2000-126766

Accordingly, it is an object of the present invention to provide an industrially efficient method for treating a developing waste liquid containing a tetraalkylammonium ion, which is a method of treating a developing waste liquid containing a tetraalkylammonium ion, even if The cation exchange resin or the chelating resin used in the treatment of the development waste liquid is repeatedly subjected to regeneration treatment, and cracking and early deterioration do not occur.

The present inventors conducted a dedicated review to achieve the above objectives. First, the inventors of the present invention reviewed the deterioration mechanism of the resin when the cation exchange resin or the chelating resin was converted from the H type to the TAA ion type. As a result, it was found that when a TAA ion solution having a high TAA ion concentration is used, swelling due to the TAA ion type and rapid swelling due to neutralization heat occur, which promotes Deterioration of the above resin. According to the above knowledge, it has been found that the cation exchange resin or the chelating resin which has been contacted with an acid to be contacted with H is contacted with water until the pH of the solution in which the resin is distilled is 3 or more, and the contact is made. The TAA ion solution of 0.3~0.8mol/L is converted into the TAA ion type TAA ion type conversion step, and even if a relatively high concentration TAA ion solution is used to convert into the TAA ion type, the neutralization heat can be suppressed at the same time. The present invention has finally been completed by the rapid swelling of the resin and the rapid swelling when converted into the TAA ion type.

That is, the present invention is a method for treating a developing waste liquid containing TAA ions, which comprises (1) an H-type conversion step of contacting a cation exchange resin or a chelating resin with an acid, and (2) performing an H-type conversion. The resin in the step is contacted with water until the pH of the distillate from the resin is 3 or more, and (3) the resin having undergone the acid removal step is contacted with TAA of 0.3 mol/L to 0.8 mol/L. a TAA ion-type conversion step of the ionic solution, (4) contacting the cation exchange resin or the chelating resin that has undergone the TAA ion-type conversion step with the development waste liquid containing the TAA ion to remove the image waste of the impurities in the waste liquid Liquid processing steps.

According to the method for treating a waste liquid containing TAA ions according to the present invention, when a cation exchange resin or a chelating resin used in the treatment is converted from an H-type to a TAA ion type, even if a relatively high concentration of the TAA ion solution is used, It is also possible to simultaneously prevent the sharp swelling of the resin due to the neutralization heat and the sharp swelling when converted into the TAA ion type. Therefore, the resin can be repeatedly regenerated without any increase in the amount of waste liquid during the above conversion. Therefore, it is stable and has The development waste liquid containing TAA ions is efficiently purified.

Best form for implementing the invention

The method for treating a developing waste liquid containing TAA ions of the present invention is characterized by comprising: (1) an H-type conversion step of contacting a cation exchange resin or a chelating resin with an acid, and (2) making the above-described H-type conversion step The resin is contacted with water until the pH of the distillate from the resin is 3 or more, and (3) the resin having undergone the acid removal step is contacted with a TAA ion solution of 0.3 mol/L to 0.8 mol/L. TAA ion-type conversion step, (4) contacting the cation exchange resin or the chelating resin which has undergone the TAA ion-type conversion step with the development waste liquid containing TAA ions to remove the impurity waste liquid in the waste liquid .

(Cation exchange resin or chelating resin) In the method for treating a waste liquid containing TAA ions of the present invention, examples of the cation exchange resin to be used include styrene-divinylbenzene copolymer and acrylic acid. a strongly acidic cation exchange resin having a strong acid group such as a sulfonic acid group introduced into a matrix of a divinylbenzene copolymer or a methacrylic acid-divinylbenzene copolymer, and a carboxyl group or a phenolic hydroxyl group introduced into the matrix A weakly acidic cation exchange resin of a weak acid group. The structure of the above resin is a gel type, a porous type, a high porous type, or a large network (MR) type, and any of the structures of the present invention can be suitably used. An MR type excellent in swelling shrinkage strength is particularly suitable.

Further, as the chelating resin, for example, styrene-divinylbenzene can be cited. In the copolymer, a valley of an amine sulfonic acid type, a polyamine type, or an N-methylglutamine type such as an iminodiacetic acid type, an iminopropionic acid type or an aminomethylenesulfonic acid type is introduced. A combination of a guanamine type, an amino carboxylic acid type, a dithiocarbamic acid type, a pyridine type, a thiol type, an amine oxime type, or the like.

In the method for treating a development waste liquid containing TAA ions of the present invention, any of the above cation exchange resins or chelating resins can be used. In general, depending on the type of the cation exchange resin or the chelating resin, the metal ions that can be removed are different, and therefore, they can be appropriately selected depending on the metal ions to be removed. Further, the cation exchange resin or the chelating resin may be used singly or in combination of several or more. Alternatively, a cation exchange resin or a chelating resin may be used in combination. The method of using the resin may be any one of the following methods: contacting a solution for performing the above treatment with a cation exchange resin or a chelating resin, and separating the cation exchange resin or the chelating resin by filtration or the like after stirring. a method of preparing a column packed with a cation exchange resin or a chelating resin to pass a solution for performing the above treatment from above or below the column to bring the cation exchange resin or the chelating resin into contact with the column method. . Among them, in the treatment method of the present invention, it is preferable to use a column method from the viewpoint that each step can be continuously performed.

(H-type conversion step) The above cation exchange resin or chelating resin is usually commercially available as an H-type or a sodium ion-type (Na-type). In the semiconductor manufacturing process and the like, since the incorporation of metal ions or the like is strictly restricted, the resin converted into the TAA ion type is used, and when the metal ions or the like in the developing waste liquid containing the TAA ions is removed, the Na type is used. Generally, the contact acid is converted into an H type, and then transferred. Change to TAA ion type. Further, when the resin which has been exposed to the developing waste liquid containing TAA ions is regenerated, it is necessary to contact the resin with an acid to remove impurities such as metal ions, and to convert the resin from the TAA ion type to the H type.

The acid to be contacted with the cation exchange resin or the chelating resin is not particularly limited as long as it generates hydrogen ions in the form of an aqueous solution, and examples thereof include a mineral acid aqueous solution such as hydrochloric acid or sulfuric acid. Among the above-mentioned acids, an aqueous hydrochloric acid solution is preferred from the viewpoint of industrially inexpensive availability and ease of concentration adjustment. The concentration and the amount of the hydrochloric acid to be used are not particularly limited as long as they are a sufficient concentration and amount for the conversion of the H-type and the removal of impurities such as metal ions, and are usually 3 to 10 (L/L-resin). It is sufficient that the cation exchange resin or the chelating resin is contacted with a 1 to 10% by mass aqueous hydrochloric acid solution.

In the H-type conversion step, the method of contacting the cation exchange resin or the chelating resin with the acid is not particularly limited. For example, in the case of the column method, in the column packed with the cation exchange resin or the chelating resin, It is any one of the upward flow of acid supplied from the lower side of the column or the downward flow supplied from above the column, but from the viewpoint of the ease of structure of the device or the less damage to the cation exchange resin or the chelating resin, It is preferred to pass the acid in a descending flow. Moreover, the flow rate of the acid to the column is smaller as the point of reducing the damage to the cation exchange resin or the chelating resin, but from the viewpoint of processing time and efficiency, the space velocity is preferred. (SV) = 5~20 (1/hr).

(Acid Removal Step) In the present invention, for the cation exchange resin or the chelating resin which has been subjected to the aforementioned H-type conversion step, an acid removal step in contact with water is performed until The pH of the distillate derived from the resin is 3 or more, and is important for the combination with the TAA ion-type conversion step to be described later. That is, by contacting the resin converted to the H-form with water until the pH becomes 3 or more, it is possible to contact the TAA ion solution having a relatively high concentration. When the resin in which the acid remains is directly contacted with the TAA ion solution to form the TAA ion type, the neutralization reaction proceeds rapidly. At this time, since the neutralization heat is generated, the resin is rapidly swollen. Therefore, by performing the acid removal step to remove the acid remaining in the cation exchange resin or the chelating resin, it is possible to suppress the rapid swelling of the resin due to the occurrence of the neutralization heat when converted into the TAA ion type.

In the acid removal step of the present invention, when the pH of the distillate from the resin is 3 or more, the subsequent conversion to the TAA ion type can sufficiently suppress the occurrence of the neutralization heat, but is surely removed. From the viewpoint of suppressing damage to the above resin, it is more preferred that the pH of the distillate is 5 or more.

Further, in the treatment of the development waste liquid containing the TAA ions, it is preferred that the water used in the acid removal step has a conductivity of 0.1 μS/cm or less from the viewpoint of strictly restricting the mixing of metal ions or the like. . As such water, ion-exchanged water and ultrapure water can be illustrated.

The method of contacting the cation exchange resin or the chelating resin with water in the acid removal step is not particularly limited, and the same contact method as the above-described H-type conversion step can be employed. For example, in the column method, the contact direction of water may be either an upflow or a downflow. Moreover, the flow rate of water to the column is reduced from the point of reducing the damage to the cation exchange resin or the chelating resin, but from the point of view of processing time and efficiency, SV= is preferred. 5~ 20 (1/hr).

(TAA Ionization Conversion Step) In the method for treating a waste liquid containing TAA ions of the present invention, the concentration of the TAA ion in contact with the cation exchange resin or the chelating resin subjected to the acid removal step is 0.3 mol/L. It is important to convert the TAA ion solution of 0.8 mol/L into a TAA ion type conversion step of converting to a TAA ion type. That is, when the TAA ion concentration is less than 0.3 mol/L, when the cation exchange resin or the chelating resin is converted into the TAA ion type, the required TAA ion solution is increased, and in the above TAA ion type conversion step, The amount of waste liquid discharged has also increased, and it cannot be said that it is industrially efficient, so it is not suitable. In addition, when a TAA ion solution having a concentration lower than 0.3 mol/L is used and the amount of use is reduced, the resin is converted into a TAA ion type, and the metal ions in the developing waste liquid containing TAA ions are adsorbed and removed. When the impurities are present, the removal efficiency is lowered. On the other hand, when the TAA ion concentration exceeds 0.8 mol/L, for example, even if the acid removal step is carried out, the rapid swelling of the above resin cannot be suppressed. Further, the TAA ion concentration of the TAA ion solution is particularly preferably from 0.3 mol/L to 0.5 mol/L from the viewpoints of high operational efficiency and high effect of suppressing rapid swelling of the resin.

The TAA ion solution used in the present invention is not particularly limited as long as it is an aqueous solution containing TAA ions. For example, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylate is preferably used. A TAAH aqueous solution of a hydroxide of TAA ions such as a quaternary ammonium ion. Further, when the cation exchange resin or the chelating resin is a strongly acidic cation exchange resin, it is also preferred to use an aqueous solution of the TAA ion salt as the TAA ion solution. As the TAA away Examples of the counter ion of the sub-salt include a chloride ion, a fluoride ion, a bromide ion, a carbonate ion, a bicarbonate ion, and the like. Among the above TAA ion solutions, an aqueous solution of a tetramethylammonium hydroxide aqueous solution and a tetramethylammonium salt can be preferably used from the viewpoint of widely used as a developing solution in a semiconductor process.

Further, the amount of the TAA ion solution to be used in contact with the cation exchange resin or the chelating resin is not particularly limited as long as it can be converted into a sufficient amount of the TAA ion type, and can be appropriately selected. In the case of the above-described column method, it is sufficient to bring the above resin into contact with 3 to 10 (L/L-resin).

In the TAA ion-type conversion step, the method of contacting the cation exchange resin or the chelating resin with the TAA ion solution is not particularly limited, and the same contact method as the above-described H-type conversion step can be employed. For example, in the column method, the contact direction of the TAA ion solution may be either an upflow or a downflow. Moreover, the flow rate of the TAA ion solution to the column is smaller as the point of reducing the damage to the cation exchange resin or the chelating resin, but from the viewpoint of processing time and efficiency, it is preferably SV=5~20 (1/hr).

(Drawing Waste Liquid Treatment Step) In the method for treating a waste liquid containing TAA ions of the present invention, the resin having undergone the TAA ion-type conversion step is subsequently contacted with a development waste liquid containing TAA ions, A developing waste liquid treatment step of removing impurities such as metal ions in the waste liquid.

As described above, the development waste liquid containing TAA ions mainly contains an organic substance derived from a photoresist such as a novolak resin and TAAH. The developing waste liquid generally exhibits an alkaline pH of 12 to 14, and an organic substance derived from a photoresist is alkaline. The developing waste liquid is dissolved in a salt form with TAA ions by an acid group such as a carboxyl group. Further, the above-described TAA ion-containing developing waste liquid is neutralized by an acid such as hydrochloric acid or carbonic acid gas, and is removed by filtering the insoluble organic material from the photoresist. In this case, the TAA ion in the above-mentioned developing waste liquid is present as a salt of another anion derived from an acid. For example, when neutralized with carbonic acid gas, the TAA is present as a carbonate or bicarbonate.

In the present invention, the development waste liquid containing the TAA ion containing the organic substance derived from the photoresist may be a development waste liquid containing TAA ions which is neutralized by carbonation gas or the like to remove the organic substance derived from the photoresist. It can be used without any particular limitation. However, from the viewpoint of suppressing the residual of the organic substance derived from the photoresist in the above resin, it is preferred to use a developing waste liquid containing TAA ions which is neutralized by carbonation gas or the like to remove the organic substance derived from the photoresist.

In the developing waste liquid treatment step of the present invention, the TAA ion concentration in the developing waste liquid used and the treatment amount of the waste liquid are not particularly limited, and the removal of impurities such as metal ions in the above resin can be considered. Efficiency, etc., make appropriate choices. For example, even if a developing waste liquid having a TAA ion concentration higher than the TAA ion solution is used, the cation exchange resin or the chelating resin can be used without cracking or pulverization.

In the above treatment, the contact method of the cation exchange resin or the chelating resin with the development waste liquid is not particularly limited, and the same contact method as the above-described H-type conversion step can be employed. For example, in the column method, the contact direction of the above-described developing waste liquid containing TAA ions may be either an upflow or a downflow. Further, the flow rate of the developing waste liquid to the column is preferably SV = 5 to 20 (1/hr) from the viewpoint of processing time and efficiency.

(Alkali Washing Step) In the cation exchange resin or the chelating resin which has been subjected to the above-described developing waste liquid treatment step, impurities such as metal ions remain. The impurities can be removed from the resin by the aforementioned H-type conversion step. However, in the above resin, an organic substance derived from a photoresist remains in addition to an impurity such as a metal ion, and the organic substance is precipitated by an acid, which causes clogging or deterioration of the resin. Therefore, it is preferred to carry out the alkali before the H-type conversion step. Washing steps. By performing the alkali washing step, the organic substance derived from the photoresist adsorbed on the above resin can be dissolved and removed.

The alkali to be used in the alkali washing step is not particularly limited as long as it can dissolve the organic substance derived from the photoresist, and an inorganic base such as sodium hydroxide or potassium hydroxide or an organic base such as TAAH can be appropriately selected. Among them, from the viewpoint of the removal efficiency of the organic substance from the photoresist, from the viewpoint of preventing the incorporation of the inorganic cation, etc., TAAH is preferable. When the concentration of the above-mentioned alkali is too low, when an organic substance derived from a photoresist is removed from a cation exchange resin or a chelating resin, a large amount of an alkali solution is required, and the amount of waste liquid is also increased, which cannot be said to be efficient in the industry. It is not appropriate. In addition, when it is too high, it is easy to cause rapid shrinkage or swelling of the above-mentioned resin due to the alkali washing step when neutralizing the developing waste liquid of the organic substance derived from the photoresist by neutralizing with an acid such as carbonic acid gas. It is the main cause of resin deterioration. Therefore, the concentration of the alkali in the alkali washing step is preferably from 0.3 mol/L to 0.8 mol/L. The amount of the alkali solution in the alkali washing step is not particularly limited as long as it is a sufficient amount to remove the organic substance derived from the photoresist, and can be appropriately selected.

In the above alkali washing step, a cation exchange resin or a chelating resin and The contact method of the alkali solution is not particularly limited, and the same contact method as the above-described H-type conversion step can be employed. For example, in the column method, the contact direction of the alkali solution may be either an upflow or a downflow. Further, the flow rate of the alkali solution to the column is preferably SV = 5 to 20 (1/hr) from the viewpoint of the treatment time and efficiency.

(Cycle Step) In the method for treating a waste liquid containing TAA ions of the present invention, the cation exchange resin or the chelating resin which has been subjected to the above-described alkali washing step is carried out by recycling to the aforementioned H-type conversion step. The cycle step can be repeated as a TAA ion type. In the present invention, particularly in the TAA ion-type conversion step, sharp swelling of the above resin can be prevented, and as a result, occurrence of cracking or pulverization can be prevented in the resin. Therefore, the resin can be repeatedly regenerated, and the developer waste liquid containing TAA ions can be removed by metal ions or the like by a cation exchange resin or a chelating resin, and industrially efficient from the viewpoint of processing cost and the like. Conducted.

[Examples]

In order to more specifically illustrate the method of the present invention, the embodiments are set forth below, but the invention is not limited by the embodiments.

The developing waste liquid (sample 1) discharged from the liquid crystal display factory and the developing waste liquid (sample 2) discharged from the semiconductor device factory are each concentrated by an evaporation method, and then neutralized with carbon dioxide gas. The development waste liquid of the insoluble organic material from the photoresist was filtered out as a sample of the development waste liquid containing TAA ions. Each of the above samples contained an organic substance derived from a photoresist and tetramethylammonium hydroxide (hereinafter abbreviated as TMAH), and the concentration of the TAA ions was 57% by mass. Table 1 shows the water quality of sample 1 and sample 2.

Further, in the following examples and comparative examples, the degree of pulverization of the cation exchange resin or the chelating resin was measured by collecting the supernatant in the column immediately after the completion of the TAA ion-type conversion step at room temperature. After standing for 1 minute, the absorbance at 500 nm was measured with a spectrophotometer. Therefore, the larger the absorbance, the less likely it is to settle, i.e., the more resin is pulverized.

Further, the metal ion removal performance of the chelating resin after regeneration is evaluated by the residual concentration of Al ions and Fe ions in the sample after the chelating resin is passed through, and the metal ion removal of the cation exchange resin after regeneration is performed. The performance was evaluated by the residual concentration of Na ions and K ions in the sample after the cation exchange resin was passed through. The metal concentration was analyzed by high frequency inductively coupled plasma mass spectrometry (ICP-MS).

Example 1

100 mL of a chelating resin Duolite C467 (trade name: manufactured by Rohm and Haas Co., Ltd.) having an amino group-forming group as a chelating group was filled in a column. Next, it is washed by ultrapure water → H-type conversion step (1 mol/L HCl solution) → acid removal step (ultra-pure water of pH 5.7) → TAA ion type conversion step (0.5 mol/L TMAH solution) And become a TMA type.

The flow rate of each step is 5 (L/L-resin), and the space velocity at the time of liquid passage. The degree of liquid flow was SV=5 (1/hr). Moreover, after the acid removal step, the pH of the distillate was 5.7.

In the above-described TMA ion-type column, the sample 1 was passed through at 8 L (80 L/L-resin) and SV = 20 (1/hr). Next, the regeneration treatment of the chelating resin is carried out in the following order: alkali washing step (0.5 mol/L TMAH solution) → ultrapure water washing (ultra-pure water of pH 5.7) → H-type conversion step (1 mol/L) HCl solution) → acid removal step (ultra-pure water at pH 5.7) → TAA ion-type conversion step (0.5 mol/L TMAH solution).

The liquid passing amount in each step was 5 (L/L-resin), and the liquid was passed through to SV = 5 (1/hr). Further, after the acid removal step of each cycle, the pH of the distillate was 5.7. The liquid passage of the sample 1 and the regeneration of the chelating resin were regarded as one cycle, and the cycle was repeated five times in total.

The degree of pulverization after completion of the fifth cycle was 0.007 Abs, and the concentrations of Al ions and Fe ions remaining in the sample 1 of the chelating resin in the fifth cycle were 5 ppb and 2 ppb, respectively. Further, as a result of performing the sixth cycle, the pressure difference at the time of liquid passage or the decrease in the liquid passing rate did not occur, and the same results as in the fifth cycle were obtained.

Comparative Examples 1 and 2

The procedure was repeated 5 times in the same manner as in Example 1 except that the TMAH concentration in the TAA ion-type conversion step was changed to 1 mol/L (Comparative Example 1) and 0.1 mol/L (Comparative Example 2). Recycling of the circulating sample 1 and the chelating resin.

The degree of pulverization after the end of 5 cycles was 0.071 Abs (Comparative Example) 1), 0.001 Abs (Comparative Example 2). The concentration of Al ions remaining in the sample 1 of the chelating resin in the fifth cycle was 4 ppb (Comparative Example 1) and 51 ppb (Comparative Example 2), and the Fe ion concentration was 2 ppb in both Comparative Examples 1 and 2.

From this result, it is understood that when the concentration of the TAA ion solution is higher than 0.8 mol/L, although heavy metals may be removed, the resin is pulverized due to repetition of the recycling step. Further, the sixth cycle was followed by the above-described cycle, and as a result, a pressure difference or a decrease in the flow rate at the time of liquid passage due to pulverization of the resin occurred. Further, when the concentration of the TAA ion solution is lower than 0.3 mol/L, although the resin pulverization due to the repetition of the recycling step is not observed, the concentration of Al remaining in the sample 1 is high, and it is understood that the metal ion removal performance is low. . This means that the chelating resin cannot be completely regenerated, which means that the amount of TMAH solution must be increased during regeneration.

Comparative example 3

In the same manner as in Example 1, except that the acid removal step after the H-type conversion step was not carried out, the flow of the sample 1 and the chelating of the sample 1 were repeated five times in the same manner as in the first embodiment. Regeneration of resin. The degree of pulverization after the end of the 5th cycle was 0.029 Abs. In addition, the concentration of Al ions and Fe ions remaining in the sample 1 which passed the chelate resin in the fifth cycle was 4 ppb and 2 ppb, respectively.

From this result, it is understood that when the TAA ion-type conversion step is directly performed without performing the acid removal step, even if the concentration of the TAA ion solution is from 0.3 mol/L to 0.8 mol/L, the resin is pulverized due to the repetition of the recycling step. The results of the above Example 1 and Comparative Examples 1 to 3 are collectively shown in Table 2.

Examples 2 and 3

The same procedure as in Example 1 was repeated except that the TMAH concentration in the TAA ion-type conversion step was 0.3 mol/L (Example 2) and 0.7 mol/L (Example 3). The recirculation of the sample 1 and the chelating resin of the secondary cycle. The degree of pulverization after the end of the 5th cycle was 0.004 Abs in Example 2 and 0.010 Abs in Example 3. In addition, the concentration of Al ions remaining in the sample 1 of the chelating resin in the fifth cycle was 5 ppb (Example 2) and 4 ppb (Example 3), and the Fe ion concentration was 2 ppb (Example 2) and 2 ppb, respectively. (Example 3).

Example 4

In the same manner as in Example 1, except that the sample treated with the chelate resin in Example 1 was changed from Sample 1 to Sample 2, the flow of the sample 1 and the regeneration of the chelating resin were repeated five times. The degree of pulverization after the end of the 5th cycle was 0.007 Abs, and the 5th cycle of passing the chelating resin The concentrations of Al ions and Fe ions remaining in the sample 2 were 5 ppb and 4 ppb, respectively.

Example 5

The same procedure as in Example 1 was repeated except that the chelating resin in Example 1 was changed to a chelating resin Lewatit TP260 (trade name: manufactured by BAYER) having an amino group-forming group as a chelating group. The recirculation of the sample 1 and the chelating resin of the secondary cycle. The degree of pulverization after completion of the fifth cycle was 0.005 Abs, and the concentrations of Al ions and Fe ions remaining in the sample 1 of the chelating resin in the fifth cycle were 4 ppb and 2 ppb, respectively.

The results of the above Examples 2 to 5 are collectively shown in Table 3.

Example 6

50 mL of a strong acid cation exchange resin Amberlyst 15WET (trade name: manufactured by Rohm and Haas Co., Ltd.) was filled in a column. Then, by super Pure water washing → H-type conversion step (1 mol / L HCl solution) → acid removal step (pH 5.7 ultrapure water) → TAA ion type conversion step (0.5 mol / L TMAH solution), and become TMA type .

The liquid passing amount in each step was 5 (L/L-resin), and the liquid flow was carried out at a space velocity at the time of liquid passage to SV = 5 (1/hr). Further, after the acid removal step, the pH of the distillate was 5.7.

In the above-described TMA-type column, the sample 1 was passed through at 10 L (200 L/L-resin) and SV = 20 (1/hr). Next, the regeneration treatment of the strongly acidic cation exchange resin is carried out in the following order: alkali washing step (0.5 mol/L TMAH solution) → ultrapure water washing (pH 5.7 ultrapure water) → H type conversion step (1 mol /L HCl solution) → acid removal step (ultra-pure water at pH 5.7) → TAA ion-type conversion step (0.5 mol/L TMAH solution).

The liquid passing amount in each step was 5 (L/L-resin), and the liquid was passed through to SV = 5 (1/hr). Further, after the acid removal step of each cycle, the pH of the distillate was 5.7. The flow of the sample 1 and the regeneration of the cation exchange resin were taken as one cycle, and the cycle was repeated five times in total.

The degree of pulverization after the end of the fifth cycle was 0.002 Abs, and the concentration of Na ions and K ions remaining in the sample 1 of the cation exchange resin in the fifth cycle was <1 ppb. Further, as a result of performing the sixth cycle, the pressure difference at the time of liquid passage or the decrease in the liquid passing rate did not occur, and the same results as in the fifth cycle were obtained. No resin pulverization due to repetition of the recycling step was observed, and in the sample 1 after passing through the cation exchange resin, both Na ions and K ions were removed.

Comparative Examples 4 and 5

Except that the TMAH concentration in the TAA ion-type conversion step in Example 6 was 0.1 mol/L (Comparative Example 4) and 1 mol/L (Comparative Example 5), the same procedure as in Example 6 was repeated. The regeneration of the sample 1 of the secondary cycle and the strong acid cation exchange resin. The degree of pulverization after the end of the fifth cycle was 0.002 Abs (Comparative Example 4) and 0.011 Abs (Comparative Example 5). The concentration of Na ions remaining in the sample 1 which passed through the cation exchange resin in the fifth cycle was 97 ppb (Comparative Example 4) and <1 ppb (Comparative Example 5), and the K ion concentration was 58 ppb (Comparative Example 4) and <1 ppb, respectively. (Comparative Example 5).

From this result, even when the concentration of the TAA ion solution was lower than 0.3 mol/L in the cation exchange resin, no resin pulverization due to the repetition of the recycling step was observed, but the Na ion and K of the cation exchange resin were not observed. The ion removal performance is low and cannot be completely regenerated. Further, it is understood that when the ratio is higher than 0.8 mol/L, the Na and K removal performance of the cation exchange resin is not lowered, but the resin pulverization due to the repetition of the recycling step occurs. Further, after the above cycle, the sixth cycle was followed, and as a result, a pressure difference or a liquid flow rate at the time of liquid passage was lowered.

The results of the above Example 6 and Comparative Examples 4 and 5 are collectively shown in Table 4.

※Type of filled resin C... Strong acid cation exchange resin Amberlyst 15WET

Example 7

10 L of a chelating resin Duolite C467 (trade name: manufactured by Rohm and Haas Co., Ltd.) having an amino group-containing phosphate group as a chelating group was filled in a column 1 having a diameter of 150 mm and a height of 2000 mm made of transparent vinyl chloride. The resin of this column 1 is washed by ultrapure water → H type conversion step (1 mol / L HCl solution) → acid removal step (ultra pure water of pH 6.9) → TAA ion type conversion step (0.5 mol / L TMAH solution), and become TMA type.

The liquid passing amount in each step was 5 (L/L-resin), and the liquid flow was carried out at a space velocity at the time of liquid passage to SV = 5 (1/hr). Further, after the acid removal step, the pH of the distillate was 3.5.

In the above-described TMA ion-type column 1, the sample 1 was passed through at 800 L (80 L/L-resin) and SV = 10 (1/hr). Next, the regenerating treatment of the chelating resin is carried out in the following order: an alkali washing step (0.5 mol/L TMAH solution) → ultrapure water washing (ultra pure water of pH 6.9) → H-type conversion step (1 mol/L) HCl solution) → acid removal step (ultra-pure water at pH 6.9) → TAA ion-type conversion step (0.5 mol/L TMAH solution).

The liquid passing amount in each step was 5 (L/L-resin), and the liquid was passed through at SV = 5 (1/hr). Further, the pH of the distillate was 3.5 after the acid removal step of each cycle. The liquid passage of the sample 1 and the regeneration of the chelating resin were regarded as one cycle, and the cycle was repeated eight times in total. When the liquid is passed through the sample 1 by the sample 1, the distillate is received by the receiving tank 1.

The degree of pulverization after the end of one cycle is 0.002 Abs, and the first cycle The concentration of Al ions and Fe ions remaining in the sample 1 of the ring-penetrating resin was 2 ppb and 2 ppb, respectively. On the other hand, the degree of pulverization after completion of the eighth cycle was 0.007 Abs, and the concentrations of Al ions and Fe ions remaining in the sample 1 of the chelating resin in the eighth cycle were 3 ppb and 2 ppb, respectively. Further, when the ninth cycle was carried out, the pressure difference at the time of liquid passage or the decrease in the liquid passing rate did not occur, and the same results as in the eighth cycle were obtained.

Next, 10 L of a strong acid cation exchange resin Amberlyst 15 WET (trade name: manufactured by Rohm and Haas Co., Ltd.) was packed in a column 2 made of transparent vinyl chloride having a diameter of 150 mm and a height of 2000 mm. The resin of this column 2 is washed by ultrapure water → H type conversion step (1 mol / L HCl solution) → acid removal step (ultra pure water of pH 6.9) → TAA ion type conversion step (0.5 mol / L TMAH solution), and become TMA type.

The liquid passing amount in each step was 5 (L/L-resin), and the liquid flow was carried out at a space velocity at the time of liquid passage to SV = 5 (1/hr). Further, after the acid removal step, the pH of the distillate was 3.5.

In the above-described TMA-type column 2, the distillate of the receiving tank 1 obtained by passing the sample 1 to the column 1 was passed through at 400 L (40 L/L-resin) and SV = 20 (1/hr). Next, the regeneration treatment of the strongly acidic cation exchange resin is carried out in the following order: an alkali washing step (0.5 mol/L TMAH solution) → ultrapure water washing (ultra pure water of pH 6.9) → H-type conversion step ( 1 mol/L HCl solution)→acid removal step (ultra-pure water at pH 6.9)→TAA ion-type conversion step (0.5 mol/L TMAH solution).

The liquid passing amount in each step was 5 (L/L-resin), and the liquid was passed through at SV = 5 (1/hr). Furthermore, after the acid removal step of each cycle, the distillate The pH is 3.5.

The liquid passage of the distillate of the receiving tank 1 and the regeneration of the cation exchange resin obtained by passing the sample 1 through the liquid of the sample 1 were regarded as one cycle, and the total of eight cycles was repeated. When the distillate of the receiving tank 1 obtained by passing the sample 1 to the column 1 through the liquid 1 passes through the liquid, the distillate is received by the receiving tank 2.

The degree of pulverization after completion of the first cycle was 0.001 Abs, and the concentration of Na ions and K ions remaining in the distillate obtained by the chelating resin in the first cycle was <1 ppb. On the other hand, the degree of pulverization after completion of the 8th cycle was 0.002 Abs, and the concentration of Na ions and K ions remaining in the distillate obtained by the chelating resin in the 8th cycle was <1 ppb. Further, when the ninth cycle was carried out, the pressure difference at the time of liquid passage or the decrease in the liquid passing rate did not occur, and the same results as in the eighth cycle were obtained. No resin pulverization due to repetition of the recycling step was observed, and both Na ions and K ions in the distillate were removed after passing through the cation exchange resin.

The results of the above Example 7 are collectively shown in Table 5.

*TAA ion type conversion step, the liquid volume column 1 and the column 2 are both 0.5 mol/L. * The sample used for the treatment is the sample 2 ※ The type of the filled resin A... Chelating resin Duolite C467CC... Strong acid cation exchange resin Amberlyst 15WET

Reference example

5 mL of a chelating resin Duolite C467 (trade name: manufactured by Rohm and Haas Co., Ltd.) having an amino group-forming group as a chelating group was filled in a column. Next, ultrapure water washing→H-type conversion step (1 mol/L HCl solution)→acid removal step (ultra-pure water at pH 6.9) was carried out. The flow rate of the ultrapure water washing and H-type conversion steps is 5 (L/L-resin), and the liquid passing amount in the acid removal step is 10 (L/L-resin), and the space velocity at the time of liquid passage becomes SV. Pass through at = 5 (1/hr). Thereby, in the acid removal step, 5 mL of each of the distillate was sampled at the lower outlet of the column, and the pH was measured. The results are shown in Table 6.

In the acid removal step, when the ultrapure water of pH 6.9 is passed through at 5 L/L-resin or more, the pH is 3 or more.

Claims (3)

A method for treating a developing waste liquid containing tetraalkylammonium ions, which comprises the steps of: (1) a hydrogen ion-type conversion step of contacting a cation exchange resin or a chelating resin with an acid, and (2) The cation exchange resin or the chelating resin in the hydrogen ion type conversion step is contacted with water until the pH of the distillate from the resin is 3 or more, and (3) the cation exchange resin or the chelate having the acid removal step is performed. a tetraalkylammonium ion type conversion step in which a resin is contacted with a tetraalkylammonium ion solution of 0.3 mol/L to 0.8 mol/L, and (4) a cation exchange resin or a chelate which has been subjected to a tetraalkylammonium ion type conversion step The developing waste liquid treatment step of contacting the resin with the developing waste liquid containing tetraalkylammonium ions to remove impurities in the waste liquid. A method for treating a developing waste liquid containing a tetraalkylammonium ion according to claim 1, wherein the cation exchange resin or the chelating resin after the step of treating the developing waste liquid is subjected to the hydrogen ion type conversion step The cycle of cycling. A method for treating a developing waste liquid containing a tetraalkylammonium ion according to the second aspect of the invention, wherein the step of supplying the cation exchange resin or the chelating resin to the alkali is washed before the step of supplying the cycle.