TW200906732A - Method for the treatment of tetraalkylammonium ion-containing development waste liquor - Google Patents

Abstract

A method for the treatment of tetraalkylammonium ion-containing development waste liquor by conducting successively the conversion step of bringing an acid into contact with a cation-exchange resin or a chelating resin to convert the resin into a H < + > -form one, the acid removal step of bringing water into contact with the H < + > -form resin until the pH of the eluate from the resin becomes 3 or above, the step of bringing a 0.3 to 0.8mol/L tetraalkylammonium ion solution into contact with the resulting resin to convert the resin into a tetraalkylammonium-form one, and the step of bringing a tetraalkylammonium ion-containing development waste liquor into contact with the tetraalkyl- ammonium-form resin to remove impurities from the waste liquor.

Description

200906732 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a treatment method of 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. [Prior Art] In the lithography step of the process of electronic components such as a semiconductor device, a liquid crystal display, and 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 reviewing the effective use of the resource, there is a proposal for a method of regenerating a developing waste liquid containing TAA ions by removing impurities such as organic substances or metal ions derived from photoresist from the waste liquid and reusing TAAH. For example, there is a proposal to remove metal ions 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, etc. 5 200906732 In the method, the cation exchange resin or the chelating resin is adsorbed by removing metal ions or the like in the development waste liquid to remove TAAH by electrolysis. The method of removing the metal ion or the like in the development waste liquid by the cation exchange resin or the chelating resin is known to wash the cation which becomes a hydrogen ion type (H shape) due to the acid by ultrapure water. The exchange resin or the chelating resin is then brought into contact with TAAH at a concentration of 1 mol/L to form a tetrazolium ion type (TAA ion type), and then contacted with the above-mentioned developing waste liquid containing TAA ions to remove metal ions or the like. The method of impurities. Further, a method for regenerating the cation exchange resin or the chelating resin is proposed for the resin after contacting the development waste liquid, and the metal ion or the like is removed from the cation exchange resin or the chelating resin by contact with an acid. 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 swell is swollen due to the increase in the water content in the resin. Therefore, if the bismuth and bismuth ion type conversion is repeated, the resin is Repeated shrinkage and swelling 'cracks, the resin will smash. 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 developing waste liquid containing cerium ions is directly treated in a cerium-type cation exchange resin or a chelating resin, and the ruthenium ion is desorbed by an acid or the like after the ruthenium ion is adsorbed and treated by the resin. When the method of treating the waste liquid of the ion is used, as the development waste liquid, ΤΑΑ 200906732 == is: 〇16m°1/L or less (0. 015 mass% or less), waste, night, shovel The method is characterized in that the swelling of the resin is suppressed by using a thin TAA ion, and when the TAA ion type is regenerated, the resin can be suppressed from being sharply exchanged or chelated, and the cation exchange can be effectively suppressed. Deterioration of the tree moon. However, it is necessary to use a thin solution as a waste, such as an increase in the amount of waste liquid, and a treatment efficiency. also,

When the developing waste liquid treated by the ίίί is at a high concentration, it is necessary to add water and the like, 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 SUMMARY OF INVENTION Problems to be Solved by the Invention: II:::" To provide industrial efficiency A method for treating a waste 16-transfer solution containing tetranes, which is a means for solving the problem in the treatment of the development waste liquid in the treatment method of the cation separation + used for the separation of the tetraalkylamide In order to achieve the above object, the monthly review of the deterioration mechanism of the resin was carried out, and it was found that when the TAA ion solution having a high m ion concentration was used, the swelling caused by the 2-ion type occurred and the neutralization occurred. Rapid turbulence caused by heat, which promotes the deterioration of the above resin of 200906732. According to the above knowledge, it is found that the cation exchange resin or the chelating resin which has been in contact with the acid to be in contact with the acid contacts the water until the resin is Acid removal step when the pH of the solution is 3 or more

And, to contact the 〇. 3~0. 8mol / L TAA ion solution to convert to TAA

The ion-type TAA ion-type conversion step can simultaneously suppress the sharp swelling of the resin due to neutralization heat and convert to the TAA ion type even when a relatively high concentration of TAA ions/valley/night is used to convert to the TAA ion type. The rapid swelling has finally completed the present invention. That is, the present invention is a method for treating a developing waste liquid containing TAA ions, which is characterized by comprising (1) a ruthenium-type conversion step of bringing a cation exchange resin or a chelating resin into contact with an acid, and (2) performing an η-type conversion. The resin in the step is contacted with water until the pH of the deuterated liquid from the resin is 3 or more. [3] The resin having been subjected to the acid removal step is contacted. 3 mol/L to 〇·8m〇i /A TAA ion-type conversion step of the TAA ion solution, (4) contacting the cation exchange resin or the chelate resin having undergone the TAA ion-type conversion step with the development waste liquid containing TAA ions to remove impurities in the waste liquid The imaging waste liquid processing step. Advantageous Effects of Invention According to the method for treating a waste liquid containing TAA ions according to the present invention, when the _ sub-exchange resin or chelation used in the treatment is converted from a Η type to a ΤΑΑ ion type, even if it is used relatively high The concentration of the cerium ion solution, = can simultaneously prevent the sharp swelling of the resin caused by the neutralization heat and the sudden expansion of the ionic type, so the above conversion does not accompany the increase of the amount of waste liquid 'reproducible regeneration The resin is treated. Therefore, the developer waste liquid containing TAA ions can be efficiently purified by mosquitoes and with 200906732. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The method for treating a developing waste liquid containing cerium ions according to the present invention is characterized by comprising: (1) a step of converting a cation exchange resin or a chelating resin into contact with an acid, ( 2) an acid removal step in which the resin having undergone the Η-type conversion step is brought into contact with water until the pH of the distillate from the resin becomes 3 or more, and (3) the resin having undergone the acid removal step is brought into contact with 0.3 mol/ L~0. 8mol/L TAA ion type conversion step of the TAA ion solution, (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 The imaging waste liquid treatment step of impurities 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 and shrinkage strength is particularly suitable. Further, as the chelating resin, for example, an amine such as an imidodiacetic acid type, an iminopropionic acid type or an aminoarylenesulfonic acid type may be introduced into the styrene-divinylbenzene 200906732 copolymer. A glutamic acid type, a polyamine type, a N-mercaptoglutamine type, a glutamine type, an amino carboxylic acid type, a di-halogenated amine phthalic acid type, a bite type, a thiol type, an amine type, etc. The combination of the formation. In the method for treating a development waste liquid containing TAA ions of the present invention, any of the above cation exchange resins or chelate waxes may be used. Generally, the amount of metal ions that can be removed is different depending on the type of ion exchange resin or chelating resin, so it can be selected according to the desired dip; M miscellaneous stems... cation exchange resin or #合:=2 It can also be used alone or in combination with a cation exchange resin or a chelating resin. As a method for the above-mentioned resin, it is possible to use a method in which the solution for performing the above treatment is brought into contact with a cation exchange resin or a t-resin, and the cation j resin or the chelate tree is separated by over-rotation. Batch method, or a plug that is difficult to fill with a cation exchange resin or a chelating resin, so that the inlet and the nucleation solution are contacted from the tube with the cation exchange resin or the chelating resin r =: See === (H-type conversion step) The above cation exchange resin or whole human type (Na type) is commercially available. In the semi-conducting system, the metal ion or the like is separated by yttrium or sodium. Therefore, due to the strict limit: when the binary ion containing TM ions is used: =, if it is a type, it is generally: night ^ Metal ions and the like are contacted with acid to be converted into H type, and then transferred to 200906732 for TAA, subtype. When the above-mentioned resin which has been exposed to the developing waste liquid containing TM ions is regenerated, it is necessary to bring the resin into contact with an acid to remove impurities such as metal ions and to convert the resin from the TAA ion type to the Η type. The acid which is in contact with the resin or the chelating resin is not particularly limited as long as it generates hydrogen ions from the state of the aqueous solution. For example, T is an aqueous solution of a mineral acid such as an acid or sulfuric acid. Among the above-mentioned acids, the point of industrial availability and the ease of concentration adjustment are the best, aqueous hydrochloric acid solution. The concentration and the amount of (4), as long as it is 4 Ί conversion and removal of sufficient concentration and amount of impurities such as metal ions, that is, the spot is lacking in the above-mentioned H-type conversion step towel, the cation exchange resin money tree r == = :: one, for example Two: The supply below the camp column:::: or; = in the tube branch 'can be acid from the sound of the m (4) secret or the cation exchange resin or better. Moreover, the acid looks at the tube branch, so that the acid flows in a downward flow or the rate of damage of the chelating resin. From the point of reducing the cation exchange resin and the efficiency: the smaller the better, but the processing time is better. Good space velocity (sv) = 5~2 〇 (1/hr). (Acid removal step): 阳离子::: The cation tree ruthenium in the front Μ type conversion step is subjected to an acid removal step in contact with water until the pH of the resin from the resin of 200906732 becomes 3 or more. The combination of the TAA ion type conversion steps described later is important. That is, by contacting the resin which has been converted into a ruthenium type with water until the pH becomes 3 or more, it is possible to contact a relatively high concentration of the TM ion solution. When the above-mentioned resin in which the acid remains is directly contacted with the TAA ion solution to become the TAA ion type, the neutralization reaction proceeds rapidly. At this time, the above-mentioned resins are swollen due to the generation of the neutralization heat. 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 sharp swelling of the resin due to the occurrence of the neutralization heat when converted into the cesium ion type. In the acid removal step of the present invention, when the enthalpy of the distillate from the resin is 3 or more, the subsequent conversion to the ταα ion type can sufficiently suppress the occurrence of the neutralization heat, but it is surely From the viewpoint of the damage to the above resin, it is more preferable that the pH of the liquid is 5 or more. Further, in the treatment of the development waste liquid containing TAA ions, the water used in the acid removal step has a conductivity of 0·1 /z S/cm or less from the viewpoint of restricting the mixing of metal ions or the like. The water is better. As such water, ion-exchanged water and ultrapure water can be exemplified. The method of contacting the cation exchange resin or the chelating resin with water in the above acid removal step is not particularly limited, and a contact method with the above-mentioned "second step" can be employed. For example, in the column method, the contact direction of water. ' Any type of upflow or downflow. Further, the water-to-tube (four) liquid-feeding speed can be reduced from the point of reducing the damage to the cation exchange resin or the chelating resin, but the smaller the better, but from the viewpoint of processing time and efficiency, it is preferably sv_5 = 12 200906732 20 (l/hr). (TAA ion-type 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 〇. 3m〇i /L~〇. It is important to convert the TM ion solution of 8m〇1/L into a TAA ion type conversion step of TAA ion type. That is, if the TAA ion concentration is lower than 〇.3m〇l/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 TM ion type conversion step In the middle, the amount of waste liquid discharged is 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 ion in the developing waste liquid for adsorbing and removing ions is removed. In the case of impurities, for example, two: 1* faces are removed, and if the TAA ion concentration exceeds G.8 mol/L, it is swollen. Further, the above TAA method suppresses the TAA of the AA ion solution of the above-mentioned resin, the Cao, the efficiency, and the suppression of the sharpness of the resin. .3-/L~. .5inol/L. The effect, from the point of view, is particularly good for the TAA ion solution used in the present invention, =: _ can be ': _ other limitations, such as ion-based sigma, tetraethyl shop, tetra-propyl is the use of heart-shaped four The hydroxide of the _ water ^ ^ butyl money ion f for the wax or chelating resin for the _ cation exchange / 'when the cation ion salt water as a TAA solution when 'use twist. Examples of the relative ion of the 7X1 from 13 200906732 subsalt include a vaporization ion, a fluoride ion, a bromide ion, a carbonate ion, a bicarbonate ion, and the like. Among the above TAA ion solutions, it is particularly preferable to use an aqueous solution of a tetramethylammonium hydroxide aqueous solution and a tetradecyl ammonium salt from the viewpoint of widely used as a developing liquid in a semiconductor process. Further, the amount of the TAA ion to be used in contact with the cation exchange resin or the chelating resin is not particularly limited as long as it can convert the resin into a TAA ion type, and can be appropriately selected. In the above-mentioned column method, it is sufficient to bring the above resin into contact with 3 to 10 (L/L_resin). In the second embodiment, the contact method of the cation exchange resin or the entire resin with the TAA ion solution is not particularly limited. The same contact method as the above-described Η type conversion step is used. For example, when :, the contact direction of the cerium ion solution may be any one of the upflow or the downflow. Moreover, the flow rate of the cesium ion solution to the column is reduced from the point of reducing the damage to the cationic parent resin or the chelating resin, and the smaller the better, from the viewpoint of processing time and efficiency, preferably Sv=5~2〇(i^^.— (development waste liquid treatment step) The treatment method of the TAA ion-containing development waste liquid of the present invention is such that the resin having undergone the above TAA ion type conversion step is followed by the person right The imaging waste liquid of the TAA ion is contacted to remove the metal waste from the waste liquid in the waste liquid treatment step. As described above, the development waste liquid containing TAA ions is mainly contained, and the varnish resin and the like are from the photoresist. The organic matter and Li. The development waste liquid = the current pH of 12 to 14, the organic matter from the photoresist, in the imaging waste liquid of 14 200906732, by the acid group of its carboxyl group, etc. The TAA ion is dissolved in the form of a salt. Further, the above-mentioned cerium 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 substance derived from the photoresist. Next, the cesium ion in the above-mentioned developing waste liquid is taken as acid The salt of the other anion is present. For example, when neutralized with carbonic acid gas, the hydrazine is present as a carbonate or a bicarbonate. In the present invention, the above-mentioned aging waste containing cerium ions containing an organic substance derived from a photoresist The liquid itself may be a developing waste liquid containing cerium ions which is neutralized by carbonation gas or the like to remove organic substances derived from the photoresist, and may be used without particular limitation. However, from the inhibition of organic substances derived from photoresist in the above resin In view of the residual point, it is preferred to use a developing waste liquid containing cerium ions which is neutralized by carbonation gas or the like to remove the organic substance derived from the photoresist. In the developing waste liquid processing step of the present invention, the used The concentration of the cerium ion in the developing waste liquid and the amount of the waste liquid to be treated are not particularly limited, and may be appropriately selected in consideration of the removal efficiency of impurities such as metal ions in the resin, for example, even if the ratio is higher than the above. The imaging waste liquid with a high cerium ion concentration in the ionic solution can also be used in the case where the cation exchange resin or the chelating resin is not cracked or pulverized. In the 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 Η type conversion step can be employed. For example, in the column method, the above-mentioned cesium ion is contained. The contact direction of the developing waste liquid may be any one of an upflow or a downflow. Further, the flow rate of the above-mentioned developing waste liquid to the column is preferably SV=5 from the viewpoint of processing time and efficiency. ～20(l/hr) 15 200906732 (alkaline cleaning step) In the cation exchange resin or the chelating resin which has been subjected to the above-described development waste liquid treatment step, impurities such as metal ions remain. The resin is removed from the resin by the Η-type conversion step. However, in the resin, an organic substance derived from a photoresist remains in addition to impurities such as metal ions, and the organic substance is precipitated by acid, which causes clogging or deterioration of the resin. Therefore, it is advisable to perform a washing step before performing the Η type conversion step. 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 hydrazine can be appropriately selected. Among them, from the viewpoint of the removal efficiency of the organic substance derived from the photoresist, from the viewpoint of preventing the incorporation of inorganic cations, etc., it is preferably ruthenium. 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 test solution in the washing step is not particularly limited as long as it is a sufficient amount to remove the organic substance from the photoresist, and can be appropriately selected. In the above alkali washing step, the contact method of the cation exchange resin or the chelating resin with the base solution of 16 200906732 is not particularly limited, and the same contact method as the above-described Η 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 (l/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 above-described Η type conversion step. The cycle step, and can again become a cesium ion type. In the present invention, in particular, when the ruthenium ion type conversion step is carried out, the above-mentioned resin can be prevented from being drastically swollen, and as a result, occurrence of cracking or pulverization can be prevented in the resin. Therefore, the above-mentioned resin can be repeatedly regenerated, and a cation exchange resin or a chelating resin can be used to remove a metal ion or the like from a developing waste liquid containing cerium ions, and it is 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 following examples are set forth, but the present invention is not limited by the examples. 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 developing waste liquid of the insoluble organic material from the photoresist was filtered out as a sample of the developing waste liquid containing cerium ions. Each of the above samples contained an organic substance derived from a photoresist and tetramethylammonium oxide (hereinafter referred to as ruthenium), and the concentration of ruthenium ions was 57% by mass. 17 200906732 Table 1 shows the water quality of sample 丨 and sample 2 [Table 1] A1 Fe '_ Na (ppb) (ppb) (ppb) Sample 1 332 63 —-- 149 Sample 2 542 —---1 77 378

114

In the case of the chelate tb, the degree of cation exchange resin or chelation is determined by collecting the column (4) supernatant immediately after the TA f beam, and measuring at room temperature by static light == clock light. The absorbance at ° nm was carried out. Therefore, it is said that the more difficult it is to settle, the more the resin is pulverized. Further, the metal ion removal performance of the chelating resin after regeneration is the A1 ion and the k ion residue in the sample after the chelating resin is passed through: !: 'The metal ion of the cation exchange resin after regeneration The removal was evaluated by the residual concentration of ions and ions in the sample after the cation exchange resin was passed through. The metal concentration was analyzed by a high frequency inductive coupled plasma mass spectrometry (ICP-MS) method. Example 1 100 mL of a chelate tree having an aminophosphoryl group as a chelating group was deposited on a column by a Duolite C467 (trade name: manufactured by Rohm and Haas Co., Ltd.). Next, the ultra-pure water is washed to the H-type conversion step (lm〇1/L of the HC1 solution) to the acid removal step (ultra-pure water of pH 5.7) - the τΑΑ ion type conversion step (G. 5 mol/L ΤΜΑΗ solution), and become m-type. The liquid passing amount of each step was 5 (L/L-resin), and the liquid was passed through at a space velocity of 200906732 when the liquid was passed through, and SV 5 (1/hr). Further, the pH of the distillate after the acid removal step was 5.7. In the above-mentioned column which became TMA ion plastic, the sample 1 was passed through a solution of 8 L (80 L/L-resin). Next, the regeneration treatment of the chelating resin is carried out in the following order: alkali washing step (〇5m〇1/L TMAH solution)~ ultrapure water washing (pΗ5·7 ultrapure water)—n-type conversion step (lmol /L HCl solution)_&gt; Acid removal step (pΗ5.7 ultrapure water 离子 ion conversion step (〇. 5m〇i/L ΤΜΑΗ solution). The amount of liquid in each step is 5 (L/L) _ resin), the liquid was passed in as sv = 5 (1/hr). Further, after the acid removal step of each cycle, the pH of the solution was 5, 7. The liquid and the chelate of the sample 1 were used. The regeneration of the resin was repeated as a single cycle, and the cycle was repeated five times. The degree of pulverization after the end of the fifth cycle was 〇7 Abs, and the A1 remaining in the sample 1 of the chelating resin in the fifth cycle The ion and Fe ion concentrations were 5 ppb and 2 ppb, respectively. The results of the sixth cycle were as follows: The pressure difference at the time of liquid passage or the decrease in the liquid flow rate did not occur, and the same results as in the fifth cycle were obtained. Example 1 and 2 In addition to the TMA ion-type conversion step in Example 1, the TMAH concentration was changed to 1 mol/L (Comparative Example 1) and 0.1 mol/L (Comparative Example 2). In addition, the liquid passage of the sample 1 and the regeneration of the chelate resin were repeated five times in the same manner as in Example 1. The degree of pulverization after the end of the fifth cycle was 〇.〇71Abs (Comparative Example 19 200906732 1) 0.001 Abs (Comparative Example 2). The concentration of A1 ions remaining in the sample 1 of the chelating resin in the fifth cycle was 4 ppb (Comparative Example 1}, 51卯b (Comparative Example 2), and the Fe ion concentration was In Comparative Example 2, both are 2卯b. From this result, it can be seen that 'the concentration of the TAA ion solution is more than 88 mol/L. Although it is possible to remove heavy metals, the pulverization of the resin is caused by the repetition of the recycling step. After the above cycle, the sixth step of the %' result is caused by a decrease in the pressure difference or the liquid catching degree due to the pulverization of the resin. Further, the concentration ratio of the TAA ion solution is 〇.3 mol/L. When it is low, 'there is no resin pulverization due to the repetition of the recycling step', but the concentration of A1 remaining in the sample 1 is high, and it is understood that the removal of the metal ions is low. This means that the chelating resin cannot be completely regenerated, which implies When regenerating, it must increase the flow of TMAH solution. Comparative Example 3 In the same manner as in Example 1, except that the acid removal step after the Η-type conversion step was not carried out, the sample 1 was repeated in the same manner as in Example 1 Regeneration of the liquid and the chelating resin. The degree of pulverization after the end of the 5th cycle is 〇·〇29Abs. Further, the concentration of ΑI and Fe ions remaining in the sample 通过 of the chelating resin of the 5th - 楯 ring The results are 4 ppb and 2 ppb. The results show that 'the concentration of the TAA ion solution is 〇. 3m〇i/L 〇.8m〇l/L when the TAA ion conversion step is performed directly without the acid removal step. Also, 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. 20 200906732 [Table 2] The type of sample filling resin used for the treatment. The acid removal step TMAH solution (mol/L) The pulverization of the resin (Abs) Metal removal 10. (P1 隹子去t energy 3b) A1 Fe Example 1 Sample 1 A has 0. 5 0. 007 5 2 Comparative Example 1 Sample 1 A has 1 0. 071 4 2 Comparative Example 2 Sample 1 A has 0. 1 0. 001 51 2 Comparative Example 3 Sample 1 A No 0. 5 0. 029 4 2 * Type of filled resin A··· Chelating resin Duolite C467 Examples 2 and 3 The TMAH concentration at the time of the TAA ion-type conversion step in Example 1 was 0.3 mol/L (Example 2) In the same manner as in Example 1, the liquid passage of the sample 1 and the regeneration of the chelating resin were repeated five times in the same manner as in Example 1 except for 0.7 mol/L (Example 3). The comminuted degree after the end of the 5th cycle is 0. 004Abs, and the embodiment 3 is 0. OlOAbs. In addition, the A1 ion concentration remaining in the sample 1 of the chelate 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 chelating resin in Example 1 was changed from the sample 1 to the sample 2, the liquid passing through the sample 1 and the chelating resin were repeated five times in the same manner as in the first embodiment. regeneration. The degree of pulverization after the end of the fifth cycle was 0. 〇〇7Abs, and the concentration of A1 ions and Fe ions remaining in the sample 2 of the 2009-0632 sample 2 in the fifth cycle was 5 ppb and 4 ppb, respectively. Example 5 The same procedure as in Example 1 was carried out 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 as a chelating group. The liquid passage of the sample 1 and the regeneration of the chelating resin were repeated five times. The pulverization degree after the end of the fifth cycle was 0.005 Abs, and the concentrations of A1 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. [Table 3] The type of the sample-filled resin used for the treatment, whether or not the acid-removing step, the TMAH solution (mol/L), the pulverization of the resin (Abs), the metal ion removal performance (ppb), the A1 Fe, the sample 1, the sample 1 A, 0. 3 0. 004 5 2 Filling Example 1 A having 0. 7 0. 01 4 2 Example 4 Sample 2 A having 0. 5 0. 007 5 4 Example 5 Sample 1 B having 0. 3 0. 005 4 2 ※ filling Type of Resin A··· Chelating Resin Duolite C467 B.. Chelating Resin Lewatit TP260 Example 6 50 mL of a strongly acidic cation exchange resin Amberlyst 15WET (trade name: manufactured by Rohm and Haas Co., Ltd.) was filled in a column. Then, by ultra 22 200906732 pure water washing - Η type conversion step (lm 〇 1 / HCl solution) - acid removal step (p Η 5 · 7 ultrapure water) ~ ΤΜ ion type conversion step (〇 5m 〇 1 /L TMAH solution)' and become tma type. The liquid passing amount in each step was 5 (L/L-resin), and the liquid flow rate was SV = 5 (l/hr) at the space velocity at the time of liquid passage. 5。 The pH of the distillate was 5.7. In the above-described TMA-type column, the sample 1 was passed through at 1 〇L (2〇〇L/L_树曰) and SV=20 (l/hr). Next, the regeneration treatment of the strongly acidic cation exchange resin is carried out in the following order: alkali washing step (purification of AH5m〇1/L TMAH solution ultrapure water (pH 5.7 ultrapure water η type conversion step (lmol/L) HC1 &gt; trough liquid) - acid removal step (pjj5.7 pure water) - TAA ion type conversion step (〇. 5m〇i / L TMAH solution). The amount of liquid in each step is 5 (L And the pH of the distillate is 5.7. The solution of the sample 1 is passed through the liquid removal step after the acid removal step of each cycle. The regeneration of the cation exchange resin was carried out as one cycle, and the cycle was repeated five times in total. The degree of pulverization after the end of the 5th cycle was 0. Ab2Abs, and the residue of the fifth ring passed through the cation exchange resin sample i The concentration of the Na ion ions was &lt;1 ppb. Further, as a result of the sixth cycle, the pressure difference or the liquid flow rate at the time of the liquid flow did not decrease, and the same results as those of the fifth ring were obtained. The pulverization caused by the repetition of the recycling step, and the K ion in both the sample enthalpy after passing through the cation exchange resin Can be removed. + Comparative Example 4 and 5 23 200906732 In addition to the TMAH concentration at the time of the TAA ion-type conversion step in Example 6, it was changed to 0·linol/L (Comparative Example 4) and 1 mol/L (Comparative Example 5). The liquid passage of the sample 1 and the strong acid cation exchange resin which were repeated five times were repeated in the same manner as in Example 6. The degree of pulverization after the end of the fifth cycle was 〇.〇〇2Abs (Comparative Example 4). 0.011Abs (Comparative Example 5). The concentration of Na ions remaining in the sample 1 of the cation exchange resin in the fifth cycle was 97 ppb (Comparative Example 4) and &lt;1 ppb (Comparative Example 5), respectively, and the κ ion concentration was respectively 58ppb (Comparative Example 4), &lt;lppb (Comparative Example 5). As a result, it was found that even in the cation exchange resin, when the concentration of the TAA ion solution was lower than 0.3 mol/L, no cycle was observed. The resin is pulverized by the repetition of the steps, but the cation exchange resin has low Na ion and K ion removal performance and cannot be completely regenerated. Moreover, it is known that when it is higher than 〇.8m〇1/L, although Na of the cation exchange resin, K removal performance is not reduced, and occurs due to repetition of the cycle steps The resin was pulverized, and the sixth cycle was followed by the above-described cycle, and as a result, a pressure difference or a liquid flow rate at the time of liquid passage was reduced. Table 4 shows the above-described Example 6 and Comparative Examples 4 and 5. Results _ [Table 4] ----- · Type of sample filling resin used for treatment with or without acid removal step TMAH solution (raol/L) Resin pulverization (Abs) Metal ion removal performance (ppb) Example 6 Na K Sample 1 C has 0. 5 0. 002 &lt;1 &lt;1 Comparative Example 4 ---- Sample 1 C has 0. 1 0. 002 97 58 Comparative Example 5 Sample 1 C has 1 0. Oil &lt;1 &lt;;1 ※Types of filled resin 24 200906732

C... Strongly acidic 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 aminophosphoryl group as a chelating group was filled in a transparent vinyl chloride It was made into a tower 1 having a diameter of 150 mm and a height of 2000 mm. The sulphide ion conversion step (0. 5mol). The smear-type conversion step (0. 5mol). /L ΤΜΑΗ solution), and become a ΤΜΑ type. The liquid passing amount in each step was 5 (L/L-resin), and the liquid flow rate was SV = 5 (l/hr) at the space velocity at the time of liquid passage. 5。 The pH of the pH of the liquid is 3.5. In the above-mentioned TMA ion-type column 1, the sample i was passed through at 800 L (80 L/L-resin) and SV = 10 (l/hr). Next, the regenerating treatment of the chelating resin is carried out in the following order: an alkali washing step (purification of TM5m〇1/L of the TMAH solution by ultrapure water (ΡΗ6·9 ultrapure water) sH type conversion step (lmol/L HC1 solution acid removal step (pH 6.9 ultrapure water) - TAA ion type conversion step (0.5 mol / L hydrazine solution). The liquid volume of each step is 5 (L / L - resin), to become sv And the pH of the distillate is 3.5. After the acid removal step of each cycle, the liquid of the sample 1 and the regeneration of the chelating resin are regarded as In the second cycle, the cycle is repeated for 8 times. When the sample is smashed with the sample, the distillate is received by the receiving tank. The degree of pulverization after the end of the first cycle of I 1 is 0 002 Abs, and the i The concentration of the A1 ion and the Fe ion remaining in the sample 1 of the chelating resin of the ring of the second cycle is 2 ppb and 2 ppb, respectively. On the other hand, the degree of pulverization after the end of the 8 cycles is 0·〇〇7Abs, and The concentrations of A1 ions and Fe ions remaining in the sample 1 of the chelating resin in 8 cycles were 3 ppb and 2 ppb, respectively. As a result, the pressure difference or the liquid passing rate at the time of passing the liquid does not decrease, and the same result as in the eighth cycle is obtained. Next, '10 L of strong acid cation exchange resin Amberlyst 15 WET (trade name: R〇hm and Haas) The company's system is filled in a tower 2 made of transparent ethylene and having a diameter of 150 mm and a height of 2000 mm. The resin of this tower 2 is subjected to an ultrapure water washing-Η type conversion step (lm〇i/L HC1 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 amount of each step is 5 (L / L - resin), to pass The liquid at the time of the liquid is SV=5 (l/hr), and the pH of the distillate is 3.5 after the acid removal step. The sample 1 is used to receive the liquid from the turret of the barrel 1 and the shed L (the hunger/L_ resin is passed through the liquid. Then, the strong acid cation exchange resin is sequentially removed in the following order: 5 mql/L Solution solution = pure water wash (10) · 9 ultra-pure water Η type conversion step (im〇i / L leg solution acid material 9 _ pure water) 〇 (〇.5mol / The TMAH solution of L). The amount of 2 in the conversion step is 3 (L/L, fat) to become (4)·) ^, after the acid removal step of each cycle, the distillate is 26 200906732 pH The flow rate of the distillate of the receiving tank 1 and the regeneration of the cation exchange resin obtained by the sample 1 to the liquid of the column 1 was regarded as one cycle, and the cycle was repeated eight times in total. 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 &lt; lppb. On the other hand, the degree of pulverization after the completion of the 8th cycle was 0.002 Abs, and the concentration of Na ions and K ions remaining in the drug solution obtained by the chelating resin in the 8th cycle was &lt;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. [Table 5] Tower 1 Tower 2 Type of resin filled AC resin Powder metal ion removal resin Metal ion removal (Abs) Properties Pulverability (ppb) (Abs) (ppb) A1 Fe Na K Cycle number 1 0. 002 2 2 0. 001 &lt;1 &lt;1 27 200906732

* The TAA ion type conversion step is 0. 5mol/L ※ The sample used for the treatment is the sample 2 ※ The type of the filled resin A... The chelate resin Duolite C467C , Ο&quot; 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 aminophosphoryl group as a chelating group was filled in a column. Then, the ultra-pure water washing-Η type conversion step (lm〇丨

The HC1 solution acid removal step (ultra-pure water of pH 6.9). The flow rate of the ultrapure water washing and simmering type conversion step is 5 (L/L-resin), and the amount of the acid removal step is io (l/l-resin), and the space velocity at the time of liquid passage becomes sv. At the acid removal step, 5 mL of each of the distillate at the lower outlet of the column was sampled and the pH was measured. The results are shown in Table 6. [Table 6] Flow rate pH (L/L-resin) 1 1. 30 2 1. 32 3 1. 52 4 2. 28 5 3. 50 6 4. 60 7 5. 23 28 200906732 8 5. 29 9 5. 45 10 5. 70 It is understood that when the ultrapure water of pH 6.9 is passed through 5 L/L-resin or more in the acid removal step, the pH is 3 or more.

29

Claims (1)

200906732 X. Patent Application Range: 1. A method for treating a developing waste liquid containing tetraalkylammonium ions, which comprises the following steps: (1) contacting a cation exchange resin or a chelating resin with an acid hydrogen ion type (2) an acid removal step in which the cation exchange resin or the chelating resin having undergone the hydrogen ion-type conversion step is brought into contact with water until the pH of the resin from the resin is 3 or more, and (3) The cation exchange resin or the chelating resin in the acid removal step is contacted with a tetrasyl ammonium ion type conversion step of 0.3 mol/L to 0. 8 mol/L of a tetrazolium ion solution, and (4) a tetraalkyl group has been subjected to The cation exchange resin or the chelating resin of the ammonium ion type conversion step is contacted with a developing waste liquid containing tetraalkylammonium ions to remove the developing waste liquid from the waste liquid. 2. 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 process of treating the waste liquid is subjected to the hydrogen ion type conversion The cycle of cycling in the step. 3. A method of treating a developing waste liquid containing tetraalkylammonium ions according to claim 2, wherein the step of contacting the cation exchange resin or the chelate resin is performed before the step of supplying the cycle . 30 200906732 VII. Designation of Representative Representatives (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: