TW201228729A - Method for preparing tetraalkylammonium salts and preparing tetraalkylammonium hydroxide using the same - Google Patents

Abstract

In a case where tetraalkylammonium (TAA) ions are recovered from waste liquor from development or the like using a cation-exchange resin in a conventional manner, the obtained TAA salt is contaminated with metal ions. Therefore, attempts to produce TAA hydroxide using the TAA salt as raw material result in products which are significantly contaminated with metal impurities. A TAA salt solution with a low metal ion concentration can be obtained by a process which comprises bringing a solution that contains both metal ions and TAA ions, such as a waste liquor from the development of a photoresist, into contact with a cation-exchange resin to make the TAA ions adsorbed on the cation-exchange resin, and then passing an acid through the resulting cation-exchange resin to recover a TAA salt, and in which the recover is stopped before the pH of the obtained TAA salt solution lowers to a prescribed level or lower and/or before the change in the electric conductivity thereof reaches a prescribed margin or more. Further, a high-purity TAAH solution can be obtained either by bringing the TAA salt thus obtained into contact with an anion-exchange resin which has previously been converted to the OH form or by subjecting the TAA salt thus obtained to electrolysis.

Description

201228729. VI. Description of the invention: [Technical field to which the invention pertains] [0001] The present invention relates to a novel method for producing a tetraalkylammonium salt using a cation exchange resin, and a hydrogen oxyhydroxide using the same as a raw material Manufacturing method. C. Prior Art 3 [0002] In general, tetraalkylammonium hydroxide (hereinafter abbreviated as TAAH) is a standard solution for a salt base in a nonaqueous solution titration using a phase transfer catalyst as an example, or in organic synthesis. A useful compound of an organic base agent. In addition, as a processing agent for cleaning, etching, and development of a semiconductor substrate in the production of an integrated circuit or a large integrated circuit, β can be used, particularly in semiconductor applications. Since the semi-conductive substrate is sweat-stained, it is required to have high-purity germanium which is as free as possible from impurities. [0004] On the other hand, as described above, in the waste liquid used for developing the photoresist, in addition to the photoresist, metal ions and ruthenium are contained, and therefore, in order to reduce the environmental burden, the waste liquid is recovered and reused. The more important the technology is (the following is also the case where the waste liquid containing photoresist and ruthenium is called "photo-resistance waste liquid"). Heretofore, in the method of treating the photoresist developing waste liquid, the method of dispersing by the evaporation method or the reverse osmosis membrane method, and then discarding it (incineration or paying by the industry), using the activated sludge for biological decomposition treatment, and then performing the flow of the rose stream The method is mainstream. However, as described above, from the viewpoint of caring for the environment, attempts have been made to recycle the waste liquid from the waste liquid, and in many cases, for the concentrated waste liquid or the original high concentration of mH, the development is high. Waste liquid, after the neutralization of the photoresist component, electrodialysis or electricity 10014667#单号Α〇101 Page 3 of 33 1013093883-0 201228729 The method of recycling ΤΑ AH has long been widely known (see patent literature) 1 to 3) ° However, in the case of treating a waste liquid having a low concentration of TAAH, since there is a need to concentrate the TAAH waste liquid before the concentration condition of the supplyable dialysis or electrolysis is reached, it is already relative to these methods. There has been proposed a method of recovering from a photoresist developing waste liquid without performing electrodialysis or electrolysis (see Patent Document 4). In a specific method, first, a tetraalkylammonium ion (TAA ion) is adsorbed to the cation exchange resin by bringing the photoresist recording waste liquid into contact with the cation exchange resin. Next, hydrochloric acid was introduced into the cation exchange resin to recover the TAA salt, and perchloric acid was added to the obtained solution to obtain a tetraalkylammonium percarbonate (TAA percarbonate). Thereafter, the TAA peroxy acid salt is purified by crystallization, and then the obtained TAA perchlorate is brought into contact with the anion exchange resin, whereby TAAH is recovered. Further, a technique of adsorbing TAA ions onto an ion exchange resin, recovering a TAA salt from a thin developing solution, and electrolyzing it to produce TAAH is disclosed (Patent Documents 5 and 6). However, since the conditions for dissolving the TAA salt from the ion exchange resin cannot be controlled, metal ions are mixed in the obtained TAA salt solution, and as a result, there is a concentration of the solution in the solution after the electrolysis The problem of metal ions. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇4 — 6 610 2 pp. Patent Document 5: Patent No. 2688009 Patent Document 6: Special Table 2002 _5〇9〇29 Bulletin 10014667^^^^ Page 4/Total 33 Page 1013093883-0 201228729 [Summary of the Invention] <Problems to be Solved by the Invention>

[0009]

According to the above-described method, the TAa ion can be recovered at a high yield, and it is known from the review by the present inventors that there is still room for remodeling in the following points. The above method is used to measure the taa ion and the production when the TAA ion is recovered, because the recovery is still carried out until the TAA ion is reduced to 200 〇ppm, that is, the concentration is very thin, so that it is adsorbed on the cation exchange resin. All TAA ions are recovered. However, in the recovery of p, the concentration of TAA ions is decreased, and the Z acid used in the recovery is mixed in a large amount, and the metal ions adsorbed on the resin are also mixed therein, so that the obtained TAA salt contains a large amount. The problem of impurities is present. &lt;Means for Solving the Problem&gt; In order to solve the above problems, the inventors of the present invention have found that 'the TAA ion is adsorbed by contacting the photoresist recording waste liquid with the cation exchange resin, and then 'when When hydrochloric acid is introduced into the cation exchange resin to recover the TAA salt, the recovery is stopped until the pH of the obtained TAA salt solution reaches a predetermined value or less and/or the rate of change of the electrical conductivity reaches a predetermined value or more. The present invention is completed by a solution having a lower ion concentration. [〇〇1〇] That is, the present invention allows a solution containing a metal ion and a tetraalkylammonium hydroxide (TAAH) to be introduced into an adsorption column filled with a hydrogen ion-type cation exchange resin to make a tetraalkylammonium. After the ions are adsorbed on the cation exchange resin, the pH of the recovered liquid is measured and/or after the acid solution is introduced into the adsorption column to recover the recovered liquid flowing out of the adsorption column to produce a tetraalkylammonium salt. The electrical conductivity is characterized by determining the amount of recovered liquid recovered. 10014667#·单编号A0101 Page 5/33 pages 1013093883-0 201228729 [0011] Further, the present invention is to contact the TAA salt thus known to the anion exchange resin previously converted into an OH type, π Either electrolysis is performed to obtain a highly pure TAAH solution. Further, tetraalkylammonium hydroxide (TAAH) produced by using the above-described present invention is very suitable for use as a developing liquid for producing liquid crystal ruthenium or ruthenium. <Effects of the Invention> According to the method of the present invention, since the amount of recovery of the cerium salt solution is determined by a simple method of measuring the sensation and/or measuring the conductivity, it is possible to efficiently obtain cesium of high purity. salt. Therefore, in the front and rear projects, it is not necessary to provide a metal removal process using a chelating resin or the like to simplify the structure of the apparatus, thereby reducing the cost. [〇〇14] Further, a high-purity Ta ΑΗ solution can be obtained by bringing the cerium salt into contact with the anion exchange resin or by introducing the ft electrolysis. [Embodiment] The present invention is a method for producing a four-yard salt (TAA salt) from a solution containing a metal ion and a tetraalkylammonium hydroxide (TAAH), comprising contacting the TAAH solution with a cationic resin. After the taa ion is adsorbed to the cation exchange resin, the acid solution is introduced into the adsorption tower, and the pH and/or electrical conductivity of the recovered liquid flowing out of the adsorption tower is measured to determine the recovery stop timing of the recovered liquid. A method of obtaining a TAA salt. In the present invention, the solution containing a metal ion and a tetraalkylammonium hydroxide is not particularly limited as long as it is a solution containing these components (hereinafter). , called "raw material solution"). When considering the inclusion of these components and a large amount occurs in 10014667^^^51 A〇101 Page 6/33 pages 1013093883-0 201228729 semiconductor manufacturing engineering, liquid crystal display manufacturing engineering, etc., the photoresist image is discharged from the project Waste liquid is more suitable. These waste liquids are waste liquids discharged when the exposed photoresist is developed with an alkali developing solution, and mainly contain photoresist, TAAH, and metal ions. [0017] The photoresist recording waste liquid is generally alkaline with a pH of 10 to 14, and the acid group such as a carboxyl group or a phenolic hydroxyl group is dissolved by acid dissociation in a developing waste liquid having a basic photoresist. . The main component of the photoresist is exemplified by a ruthenium carboxylic acid produced by photodegradation of the azodiazepine sensitizer or a phenol derived from a phenol resin. Further, in the present invention, in the case where the above-mentioned photoresist component is contained, a part or all of the photoresist component may be removed as a target. [0018] Here, a detailed description will be given of a representative waste liquid discharged from a semiconductor manufacturing process and a developing process in the manufacture of a liquid crystal display. In the development project, an automatic developing device of a single wafer processing method is usually used. However, in this device, the process using a developing solution containing TAAH and the subsequent cleaning using pure water (substrate cleaning) can be performed in the same tank. In this case, in the cleaning process, 5 to 1 000 times of pure water of the developing solution can be used. Therefore, the developing liquid used in the developing process is usually diluted to 5 to 1 D times the waste liquid. As a result, the composition of the waste liquid discharged in this development project becomes such that TAAH accounts for 0.001 to 1 mass%, the impedance accounts for 10 to 100 ppm, and the surfactant accounts for 0 to 10 ppm. In addition, there are cases where waste liquids from other projects are mixed, and the TAAH concentration will become lower than the above range. Specifically, it may be in the range of 0.05% by mass or less (0. 001 to 0.05% by mass). In particular, in the photoresist liquid waste liquid discharged from the liquid crystal display manufacturing process, the TAAH concentration is in the range of 0.001 to 0.05% by mass, in order to produce TAA salt from such a photoresist liquid, in particular 10014667^Single number A〇101 Page 7 of 33 Page 1013093883-0 201228729 The method of the present invention can be suitably employed. [0022] In addition, a plurality of metal ions may be included in the photoresist development waste liquid. For example, in the case of monovalent ions, there are nanometers and materials; in the case of divalent ions, there are vanes, words, etc.; in the case of other multivalent ions, there are aluminum, nickel, copper, chromium, iron, etc. as photoresist liquid waste liquid. A representative metal with a large content. The TAAH in the photoresist is used in the development of the photoresist used in the production of various electronic components. In the specific example of TAAH, 'tetramethyl hydroxide hydride (hereinafter abbreviated as TMAH), tetraethyl hydride hydroxide, hydrogen emulsified tetrabutylammonium, methyl triethyl hydroxy ruthenium trioxide Ethyl ammonium, dimethyldiethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, triethyl(2-hydroxyethyl)ammonium hydroxide dihydrazinium di(2- Ethyl)ammonium, diethyldi(2,ethyl) hydroxide, methyltris(2-ethyl)hydroxide, ethyltrioxide hydroxide, ethylethylamine, hydrogen hydroxide (2-ethyl) money and the like as an example. Among them, tmah is most widely used. &lt;Engineering of Adsorption of Tetraalkylammonium Ion on Cation Exchange Resin&gt; In the present invention, a cation exchange resin in which a raw material solution as described above is filled with a hydrogen ion type (hereinafter also referred to as "Η type") is used. In the adsorption column, TA Α is adsorbed onto the cation exchange resin. That is, since the TAA ion is a cation, it is in contact with the H-type cation exchange resin, and further, the hydrogen ion of the cation exchange resin is transferred to the resin. Therefore, TAA ions can be efficiently recovered from the waste liquid. Especially in the case of waste liquid with a low concentration of ΤΑΑΙ, it is possible to recover cesium ions at low cost. 10014667#单号 A01〇i Page 8 of 33 1013093883-0 201228729 [0023] Here, since the usual metal ions are also cations, the cation exchange resin can be adsorbed through the liquid. According to the present invention, the metal ion adsorbed on the cation exchange resin and the TAA ionium are efficiently separated from each other by a method described later. Further, even in the case of a metal ion, when the ion species contained in the metal itself is anion due to a chemical equilibrium reaction such as coordination in the raw material solution, it is difficult to adsorb to the cation exchange resin and be discharged from the adsorption column. On the other hand, when the raw material solution is a photoresist waste liquid, since the organic component derived from the dissolved photoresist is usually in the form of an anion, it is difficult to adsorb to the cation exchange resin, and most of it can be removed. Further, even in the case where a nonionic component is present, in this process, since it is discharged (flowed out) without being adsorbed to the cation exchange resin, most of it can be removed. In addition, a small amount of photoresist remaining in the cation exchange resin may be washed with ultrapure water or a high-purity TAAH solution. &lt;Cation Exchange Resin&gt; In the present invention, the above cation exchange resin is not particularly limited. A known resin can be used. Specifically, any of a strongly acidic cation exchange resin having a sulfonic acid group as a sulfonic acid group and a weakly acidic cation exchange resin having a carboxyl group as a carboxyl group may be used. Among them, it is preferable to use a weakly acidic cation exchange resin from the viewpoint that the ion exchange capacity is large and the amount of the resin to be used can be lowered. Further, in the case of a weakly acidic cation exchange resin, it is also easy to carry out the elution of the TAA ions described later. [0026] In addition, the structure of the 10014667# single-numbered A〇l〇l resin is gel type or MR type (large hole type, page 9/page 33 1013093883-0 201228729)

Macroporous) resin is acceptable. The shape of the resin may be any of powder, granule, film, and fiber. From the viewpoints of processing efficiency, workability, economy, and the like, a cation-exchange resin such as a styrene-based or acrylic-based resin such as a granular material is preferably used. [〇〇27] The counter ion of the cation exchange resin is usually sold on the market as hydrogen ion (H type) or sodium ion (Na type), but in order to prevent the sodium ion from being mixed into the finally obtained TAAH solution and to enhance the TAA ion The adsorption efficiency is preferably a type in which the counter ion is set to a hydrogen ion. In the case of using a commercially available Na-type cation exchange resin, hydrochloric acid or sulfuric acid is introduced into the cation exchange resin in advance, and sufficiently washed with ultrapure water to use the counterion as a hydrogen ion. [0028] Specific examples of the strongly acidic cation exchange resin include R〇hm and

AMBERLITE IR120B, AMBERLITE IR124 manufactured by Haas, DAION SK1B, DAI0N PK228 manufactured by Mitsubishi Chemical Corporation, DU0LITE C255LFH manufactured by CHEMTEX Co., Ltd., LANWESS LEWATIT MonoPlus S100, PUROLITE PUR0LITE

Cl60 and the like as an example. In addition, specific examples of the weakly acidic cation exchange resin include AMBERLITE IRC76 manufactured by Rohm and Haas Co., Ltd., DAION WK40L manufactured by Mitsubishi Chemical Corporation, DU0LITE C433LF manufactured by Sumiyoshi CHEMTEX Co., Ltd., DU0LITE C476, and LANXESS LEWATIT CNP80WS. PUROLITE PUROLITE C104, etc. as an example. &lt;Method of Passing Solution to Adsorption Column Filled with Cation Exchange Resin&gt; 1013093883-0 In the present invention, the raw material solution is introduced into the cation exchange 10014667 which has been filled with the above-mentioned quinone type. Page 10/33 pages 201228729 The resin adsorption column is replaced with a cation exchange resin to adsorb TAA ions onto the cation exchange resin. [0030] In addition, 'for the feed solution to be filled with the cation exchange resin The method of the adsorption tower 'according to the kind or shape of the cation exchange resin, a conventional method can be suitably used. Specifically, for example, a cylindrical adsorption tower having an inflow hole at the upper portion and an outflow hole at the lower end portion is used, and the adsorption tower is filled in the adsorption tower. The cation exchange resin is preferably a method in which the raw material solution is continuously passed by gravity. In the case of this method, the size of the adsorption column is appropriately determined in accordance with the performance of the cation exchange resin. ΤΑΑ ion, such as 光 001 ~ 1% by mass of photoresist waste liquid, the height of the adsorption tower (L) The ratio of the diameter (d) is set to 0. 5~30 'The spatial velocity (SV) of the waste liquid is set to 1 (1/time) or more and 15 〇 (1/time) is more suitable. [0031 Further, the amount of the raw material liquid to be supplied is set to such an extent that it does not penetrate the cation exchange resin filled in the adsorption column, and is preferable from the viewpoint that the TAA salt can be efficiently produced by Q. [0032] Further, whether or not the TAA ions are allowed to flow out (penetrate) without being adsorbed by the raw material solution containing the cation of the cation containing the cation exchange resin or more, can be passed through the liquid which flows through the adsorption tower. The concentration of T aa ion is confirmed by ion chromatography analysis. More simply, the height of the cation exchange resin in the adsorption column can be measured. When the counter ion of the cation exchange resin changes from hydrogen ion to taa ion Although 'the volume of the cation exchange resin is different, the volume will expand to twice. Therefore, by measuring the cation exchange resin, let 4667/single reduction 101 Page/Total 33 Page 1013093883-0 2012287 In addition, when the pH of the raw material solution is 10 or more, when the pH of the raw material solution is not adsorbed and passes through the adsorption tower, the pH of the liquid that has passed through It is also possible to confirm by using a pH measuring device. In general, when TAA ions are contained in the liquid that flows out of the adsorption tower, the conductivity of the liquid increases, and it can be confirmed based on the electrical conductivity. &lt;Process for recovering tetraalkylammonium salt from cation exchange resin having adsorbed tetraalkylammonium ions&gt; In the present invention, after the TAA ion is adsorbed to the cation exchange resin by the above method, the acid solution is passed Into the adsorption column filled with the cation exchange resin, recovering the recovered liquid flowing out from the adsorption column to produce a tetraalkylammonium salt [0035], that is, introducing the acid solution from one end of the adsorption column into the adsorption tower, so that The liquid flows out from the other end to pass through, whereby excess hydrogen ions contained in the acid solution can be sequentially replaced with TAA ions, and further used as an acid salt of an acid using TAA ions. Adsorption column outflow. [0036] In the case of the acid solution, when considering the cost or the like, it is more suitable for an aqueous solution. [0037] When a usable acid is exemplified as a specific example, hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid or the like is exemplified, but from the viewpoint of easily eluting a high concentration of TAA salt, it is a strong acid. Hydrochloric acid, sulfuric acid and wall acid are suitable. Among these strong acids, the excess acid is easily removed by concentration under reduced pressure, and the material having a lower acidification force makes the liquid contact less susceptible to damage. 1001466#Item No. 1 Page 12 of 33 1013093883-0 From the viewpoint of 201228729, hydrochloric acid is most suitable. [0038] The concentration of the acid solution may be suitably selected within the range of from 1 N to 10 N, but from the viewpoint of allowing a high concentration of TAA salt to flow out and easily preventing the incorporation of metal impurities, 〇. 5N to 4N The range is particularly suitable. Further, the liquid passing rate of the acid solution may be appropriately set in accordance with the size of the adsorption tower, the type or amount of the cation exchange resin, the concentration of the acid solution, and the like, but the space velocity of the acid is preferably 1 or more and 50 or less. In the case of less than this range, the processing time will become lengthy. π v ' [0040] &lt;Recovery of effluent&gt; By introducing the above acid solution 'because the TAA ion will act as a counter ion corresponding to the acid (e.g., cr, etc.) corresponding to the acid used, and become a TAA salt adsorption Since the end of the column flows out (dissolved), the effluent can be recovered in the storage tank, and the effluent can be supplied as electrolysis to be described later. [The present invention is characterized in that the measurement of the effluent or the electrical conductivity of the effluent is such that the time at which the predetermined measurement value is reached is taken as the point at which the recovery of the enthalpy to the storage tank is stopped. Rhythm tower (4) The cationic money tree will also adsorb metal ions in addition to the m ion, but the metal can be mixed before the point where the effluent reaches a predetermined value and/or the electrical conductivity changes by more than a predetermined range. The amount of ions is suppressed to a low degree. Further, when the pH and/or the electrical conductivity of the effluent reaches the predetermined value, the state in which the liquid flows out of the adsorption tower itself may be stopped, but a flow path changing means such as a switching valve may be provided to arrive. The predetermined value. . . At the time of the point, it is suitable to recover the other storage tanks different from the above-mentioned storage tanks by the way of 10014667#&quot;early number A〇1〇l page 13/33 pages 1013093883-0 201228729. Further, the means for measuring the pH and/or the electrical conductivity is not particularly limited, and a known means can also be used. &lt;Predetermined value of pH and measurement method thereof&gt; The predetermined value of pH differs depending on the kind of acid to be used. For example, when hydrochloric acid which is a strong acid is used as the acid, since the salt which flows out, that is, vaporized TAA (hereinafter referred to as "TAAC") is neutral, the effluent is almost present in a state where TAA ions are sufficiently present in the adsorption tower. Neutral (in the case of strongly acidic cation exchange resin) or weakly to neutral (in the case of weakly acidic cation exchange resin), but as the TAA ion becomes less and less, it will slowly start to be acidic. [0046] In the case of an equilibrium state, even if the effluent is weakly acidic, the effluent contains TAA ions (TAAC) but gradually decreases, and on the other hand, with the acidity of the liquid flowing through the adsorption tower The amount of metal ions strongly adsorbed on the cation exchange resin is also gradually increased. [0047] Therefore, when the acid solution is continuously supplied, the effluent is almost free of TAA ions and contains a large amount of metal ions. Here, in the case where the recovery of TAA is emphasized, the predetermined pH value is set to be low, and when the amount of metal ions to be mixed is decreased, the setting is made higher. When a strong acid such as hydrochloric acid is used as the acid, the pH of the recovered liquid flowing out of the adsorption tower is measured, and when the pH reaches a predetermined value in the range of 3 or more and 8 or less, the recovery is stopped, whereby the recovery can be obtained. A liquid having a low concentration of metal ions contained in the TAA salt solution. In order to further set the metal ion concentration to be lower, it is preferable to set the predetermined value to pH 5 or higher. This HHU4667#单号 A0101 Page i4 / Total 33 1013093883-0 201228729 [0049] [001] [0051]

Further, by setting the predetermined value to a pH of 7 or less, the TAA salt can be recovered at a high recovery rate. Further, the term "strong acid" means an acid dissociation constant pKa of 3 or less at 25 °C. On the other hand, when the acid to be used is a weak acid such as acetic acid or carbonic acid, since the solution of the obtained TAA salt is weakly alkaline, a preferable pH range for reducing the amount of metal ion mixed may be 4~ 9. Further, the so-called weak acid means that the acid dissociation constant pKa at 25 ° C is higher than 3. In the case of measuring the pH, a conventional method can be suitably employed. Specifically, for example, the effluent flowing out of the adsorption tower is sampled in a certain amount, and the pH is measured by using a pH test paper, an electrode type pH meter, or the like, or the effluent is guided to a pipe for storage or the like, and is set. A method of measuring along a line type pH meter. If a linear pH meter is used, it is not necessary to take out the liquid on the way, and it is possible to stop the recovery at a moment when the pH reaches a predetermined value, and it is possible to suppress the loss of the recovered liquid, which is preferable. Further, although it differs depending on the pH measuring means, when the pH of the fluid is measured along the line using a general glass electrode type pH meter, the inhomogeneity of the filling state of the resin in the characteristics and in the adsorption tower is a factor. , and most likely will produce an error of ± 0.2 degrees. In the present invention, in this case, the pH value displayed by the pH meter can be statistically processed, and when the statistical value reaches a predetermined value, the effluent recovery to the storage tank can be stopped, and the statistical processing can be performed. The method is preferably a well-known processing method, for example, obtaining a value every predetermined time (for example, 0.1 second), and when the added average or the multiplied average value of the predetermined time (for example, 2 seconds) reaches a predetermined value, Set 10014667 production list & A〇101 page 15 / total page 33 1013093883-0 201228729 into a predetermined pH. Among the commercially available pH meters, there is also a pH meter having the above-described statistical processing means and a function of displaying the pH after the statistical treatment, and the pH meter can be directly used in the present invention. Further, the time interval at which the statistical processing is performed is mainly required to be changed in accordance with the flow rate (flow rate) of the effluent. When the solution is passed at a high flow rate, since the pH change of the effluent is relatively rapid, there is a need to shorten the measurement interval in order to obtain a solution in a desired state (metal ion concentration). &lt;Change rate of electrical conductivity and measurement method thereof&gt; The rate of change in electrical conductivity differs depending on the type of acid used, and also depends on the acid concentration flowing in the adsorption tower. And it is different. That is, when the acid concentration is rich, the concentration of the TAA salt contained in the effluent from the adsorption tower is relatively concentrated, and the acid concentration becomes lighter as it becomes lighter. Then, when there is sufficient TAA ions in the adsorption tower (if the flow rate is kept constant), the effluent will maintain its concentration state (hereinafter also referred to as "concentration maintenance state"). When the TAA ions sufficient to allow the acid solution to continue to flow are eluted from the cation exchange resin, the concentration of the TAA salt contained in the effluent gradually becomes smaller, and the concentration of the free acid and the metal salt increases. In this case, since the conductivity of the TAA salt solution and the electrical conductivity of the free acid and the metal salt are different, it is possible to detect the timing at which the free acid and the metal salt start to be mixed by measuring the conductivity. Specifically, tetrakisyl ammonium (TMA) is used as the TAA ion and 2N hydrochloric acid is used as the acid. When the flow rate (SV) is set to 1, the liquid flowing out from the column is four without hydrochloric acid. When the thiol vaporized ammonium (TMAC) is 80mS/cm, the maximum will rise to 500mS/cm with the mixing of hydrochloric acid. 10014667^^'^^ A〇101 Page 16 / Total 33 Page 1013093883-0 201228729 (2N hydrochloric acid). [0057] In addition, the conductivity in the concentration maintenance state varies depending on the type and concentration of the above-mentioned acid, depending on the type of the cation exchange resin, the shape of the column, the flow rate, and the like. It is necessary to confirm the operating conditions in advance. [0058] When considering the measurement accuracy of the commonly used conductivity meter (less than 1% of the whole range of soil), the shape of the column, the inhomogeneity of the filling state of the ion exchange resin, etc., the measured value of the electrical conductivity is In the case of the deviation, the fluctuation range of the electrical conductivity in the above-described concentration maintenance state is still less than ±5%. Therefore, when the conductivity exceeding the fluctuation range is considered to be rising, it can be judged that hydrochloric acid is mixed in the discharged liquid. [0059] In the present invention, in this case, the electrical conductivity value displayed by the conductivity meter can be statistically processed, and when the statistical value reaches 5% or more greater than the electrical conductivity in the concentration maintenance state, Stop the effluent recovery to the storage tank -. [0060] The method of the statistical processing only needs to adopt a well-known processing method, and for example, a value obtained every predetermined time (for example, 0.1 second) is obtained, and an average of a predetermined time (for example, between 2 seconds) is added. Or the multiplication average is set to a predetermined electrical conductivity as an example. Among the commercially available conductivity meters, there is also a conductivity meter having the above-described statistical processing means and a function of displaying the electrical conductivity after the statistical processing, and the conductivity meter can be directly used in the present invention. Further, the time interval at which the statistical processing is performed is mainly required to be changed in accordance with the flow rate (flow rate) of the effluent. When the solution is circulated at a high flow rate, since the change in the electrical conductivity of the effluent occurs more rapidly, in order to obtain a solution of the expected state of the product (metal ion concentration) of 10014667 singly & A0101 page 17 / page 33 1013093883-0 201228729 [0062] [0065] [0065] [Method for producing a ruthenium hydroxide base record from a tetraalkyl group (IV)] In the present invention, the above method is used to contain the (4) solution The TM salt is electrolyzed or made with an anion-line resin having a counter ion as a counter ion. (4) Manufacture of _ &lt;TAAH: Electrolytic Engineering of TAA Salt > For the TM salt to be obtained In the electrolysis process in which electrolysis is carried out to obtain taah, there is no limitation (four), and a known method can be used, which is suitable for the production of electrolysis using an anode, a cathode, and a sub-exchange membrane described in Patent No. m9469. . &lt;Manufacturing of bismuth: contact engineering of TAA salt and anion exchange resin. Further, the method for producing TAAH by contacting (4) m from the waste liquid back to the anion exchange resin can be used. Or the method described in 2009-1 97778. This method is a method for producing TAAH from TAAC by contacting a TAA salt with an anion exchange resin (OH type anion exchange resin) having a hydroxide ion as a counter ion. This method can easily produce high purity TAAH from TAAC without electrodialysis or electrolysis. As described above, a highly pure TAA salt can be obtained according to the present invention. Further, since the metal ion removing process such as a chelate resin is not necessary as compared with the conventional method, the total cost required for the treatment can be reduced. Further, in the case where the TAA salt is recovered from the photoresist developing waste liquid, the amount of the metal impurities can be reduced from the original amount to less than one tenth. Further, in the case of using the recovered TAA salt 1〇_7昃单号 A〇101 page 18/33 pages 1013093883-0 201228729, the obtained crucible is suitable for use in liquid crystal displays. Like liquid. [Embodiment] The following is a detailed description of the present invention, and the embodiments and comparative examples are described in detail. However, the present invention is not limited to the embodiments. Example &lt;Regeneration treatment of cation exchange resin (Η-type cation exchange resin)&gt; When used, the cation exchange resin used is filled into a glass column, depending on ultrapure water, 1N-HC1 (hydrochloric acid), and ultrapure water. The sequence is carried out by liquid and uses hydrogen ions as counter ions. Each liquid was passed through a space velocity of 5 (i/time), and the liquid amount of each liquid was set to 10 L/L-resin. &lt;Concentration measurement&gt; Tetramethylammonium hydroxide (TMAH), tetramethylammonium hydroxide (TMAC) concentration, and vapor ions can be analyzed by ion chromatography. Specifically, ICS2000 manufactured by DIONEX Co., Ltd. can be used, in which ION-pac CS12A can be used for the cation analysis, I〇N-pac AS15 can be used for the anion analysis, and the separation solution can be used for the cation analysis.玎 Use the acidity of the hospital, and the anion analysis, the solution can be analyzed using potassium aroxide. The concentration of metal ions contained in the solution can be determined by high frequency inductively coupled plasma mass spectrometry (ICP-MS) (measuring device: HP-4500 (manufactured by Agilent)) or high frequency inductively coupled plasma emission spectrometry (ICP- 〇ES) method (measurement device: iCAP 6500 DUO (manufactured by THERMO ELECTRON CORPORATION)) was measured. 10014667^^^^ A0101 Page 19 of 33 1013093883-0 201228729 The pH of the solution can be measured by a pH electrode method (measuring device: HM-30R, manufactured by Toa DKK Co., Ltd.). The electrical conductivity can be measured using a Yokogawa Electric SC measuring device (model: SC72 - 21JAA). Example 1 A weakly acidic cation exchange resin (manufactured by Mitsubishi Chemical Corporation, DIAION WK40LC) was filled in a glass column having a diameter of 22 ram x 750 ram, and the above-mentioned regeneration treatment was carried out. &lt;Adsorption Engineering of TAA Ions&gt; 8000 ml of 0.5% by mass of TMAH waste liquid (photoresist developing waste liquid, the amount of photoresist is converted to 42 ppm by COD, and the metal ion concentration is Na: 9. Oppb,

Al : 4. 4ppb, K : 1. Ippb, Ca : 12. 9ppb, Cr : 5.5ppb, Fe : 16.4ppb, Ni : 1·2 ppb, Cu : 0. 14ppb) With space velocity SV = 20(1/ Time) The liquid is passed through the column. &lt;Washing Process&gt; Subsequently, 0.5% by mass of TMAH was passed through at a space velocity of SV = 1 (1/time) to wash the impedance component. <Contact Engineering with Hydrochloric Acid/Recovery of TAAC> Next, 800 ml of 1N-HC1 was passed as a solution at a space velocity of SV = 1 (1/time), and the adsorbed TMA ions were formed into a TMAC and then dissolved. . The eluate is separately obtained in order, and can be divided into twelve kinds of liquids shown below. From 0 to 50〇11}1, 5 types are distinguished every 10 1111 (different liquids A to E); 500 to 600 ml are divided into 5 types for every 20 ml (separation of liquid F-1) ~5) ; 600 to 800ml, every 10014667^^^ A〇101 page 20/33 pages 1013093883-0 201228729 100ml to distinguish between two types (different liquid G ~ Η), a total of twelve The liquid "Measure these TMAC concentrations by ion chromatography separately by ion chromatography" measures the metal ion concentration by ICP mass spectrometry and the pH with a pH meter. The results are shown in Table 1, Figure 2, and Figure 3, respectively. [Table 1] Distinguishing pH Conductivity TMAC Concentration HC1 Concentration Metal Offset Concentration (ppb) Liquid Furnace (mS / cm) (mol /1) (mol /1) Na Al K Ca Cr Fe Ni Cu A 9.0 0 0 0 2.7 9.3 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 B SS 4S 0.63 0 10.2 &lt; 1.0 1.5 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 C S. 8 57 0.77 0 2.1 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 D 8.9 57 0.77 0 1.9 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt;0.5 &lt; 0.5 4.6 &lt;2.5 &lt; 0.3 E 8.8 58 0.78 0 t.8 8.3 &lt; 1.0 &lt; 5.0 &lt;0.5 19.3 &lt; 2.5 &lt; 0.3 F-1 8.9 56 0.76 0 U8 29.9 &lt; 1.0 &lt; 5.0 &lt;0.5 30.7 &lt; 2-5 0.7 F-2 8.8 56 0.76 0 1.9 49.9 11.6 &lt;5.0 &lt;0.5 35.7 &lt;2.5 &lt;0.3 F-3 5.3 85 0.75 0 373.7 1Π.3 17.4 230.1 &lt;0.5 86.5 &lt; 2.5 0.9 F-4 0.6 113 0.71 0.08 1333.0 245.5 92.3 2117.8 &lt;0.5 179.1 6.4 1.5 F-5 0.5 177 0.46 0.39 459.2 216.5 18.1 1091.8 &lt; 0.5 180.0 5.9 1.2 G 0.4 292 0.06 0.87 53.5 52.2 3.6 X42.2 &lt; 0.5 82.4 &lt;2.5 &lt;0.3 Η 0.3 325 0.00 1.01 11.6 9.2 1.7 14.8 &lt;0.5 26.9 &l t;2.5 &lt;0.3

As is clear from Table 1, the concentration of metal ions increased from F-3 whose pH was changed to 7 or less. The metal ion concentration of the total liquid from the liquid B to the F-2 was 1 ppb or less, the TMAC concentration was 7.8% by mass (0.71 mol/l), and the HCl content was not contained. 0%。 The TMAC recovery rate was 90.0%. [Example 2] The same operation as in Example 1 was carried out except that the acid used for the dissolution of 2N hydrochloric acid was used except that the operation of the contact engineering with hydrochloric acid was carried out under the following conditions. Get TMAC. The results are shown in Table 2. [Contact Engineering with Hydrochloric Acid/Recycling Engineering of TAAC] 10014667^ Single, No. 1 A0101 Page 21/Total 33 Page 1013093883-0 201228729 Next, 600 ml of 2N-HC1 is used as a dissolving solution at a space velocity SV = 1 (1/time) was passed through, and the adsorbed TMA ions were dissolved after forming TMAC. The eluate is separately obtained in order, and can be divided into twelve kinds of liquids shown below. From 0 to 40 0 ml, 5 types are distinguished every 80 ml (different liquids A to E); 400 to 500 ml are divided into 5 types per 20 ral (different liquids F-1 to 5); 500 Up to 600 ml, two types were separated for each 50 ml (the liquids G and H were distinguished), and the total was divided into twelve kinds of liquids. These different liquids were separately measured by ion chromatography to measure the TMAC concentration. The metal ion concentration was measured by ICP mass spectrometry, and the pH was measured with a pH meter. The results are shown in Table 2, respectively. [_][Table 2] Distinguish liquid helium pH Reinforcement (mS / cm) TMAC concentration (mol / t) HCi Concentration (mol /1) Metal tweezers concentration (ppb) Na A1 K Ca Cr Fe Mi Cu A 9.0 0 0 0 &lt; 2.5 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 β 8.8 50 0.64 0 &lt; 2.5 &lt; 1.0 IS &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt; 2.5 &lt;0.3 C 8.8 74 1,12 0 &lt;2.5 &lt;1.0 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt;4.0 &lt; 2.5 &lt; 0.3 D 8.6 76 1.17 0 &lt; 2.5 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt;0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 E 8.4 76 1-17 0 &lt; 2.5 10.3 &lt;1.0 &lt; 5.0 &lt;0.5 22.1 &lt; 2.5 &lt; 0..3⁄4 Fl 8.3 77 1.19 0 &lt; 2.5 22.8 &lt; 1.0 &lt; 5.0 &lt;0.5 33.9 &lt; 2.5 &lt; 0.3 F-2 8.2 77 1.19 0 &lt; 2.5 74.3 15.5 &lt;5.0 &lt; 0.5 39.5 &lt; 2.5 &lt; 0.3 F-3 0.8 Ϊ25 0.76 0.20 674.6 170.9 46.2 422.4 &lt; 0.5 100.1 3.0 1.3 F-4 0.3 370 0.64 1.01 1330.4 201.4 84.2 2025.0 &lt; 0.5 235.5 5.J 1.8 F-5 0.2 460 0.40 1.43 — 1.90 347.0 266.8 13,3 1008.5 &lt;0.5 186.3 4.9 1.4 G 0.1 524 0.02 220.5 78.3 5.5 188.5 &lt; 0.5 54.1 2.1 &Lt; 0.3 0.1 544 0.00 2.00 15,4 24.3 1.2 17.7 &lt; 0.5 15.9 &lt; 2.5 &lt;0.3 ------ It can be seen from Table 2 that when the pH becomes 7 or less, the metal ion concentration will rise [0080] 10014667^ Single No. 1 A0101 Example 3 using 4N hydrochloric acid as the acid used for the dissolution, except that the contact with hydrochloric acid is carried out under the conditions of the JL process, the same as in the first embodiment. Operation to get TMC. The results are shown in Table 3, page 22 of 33, 1013093883-0 201228729. <Contact Engineering with Hydrochloric Acid/Recovery of TAAC> Ο Next, 600 ml of 4N-HC1 was passed as a solution at a space velocity of SV = 1 (1/time), and the adsorbed TMA ions were formed into TMAC. Dissolution. The eluate is separately obtained in order, and can be divided into twelve kinds of liquids shown below. From 0 to 250 ml, 5 types are distinguished every 50 ml (different liquids A to E); 250 to 500 ml are divided into 5 types (different liquids F-1 to 5) for each 50 ral; 500 to In the case of 600 ml, two types (different liquids G and H) are separated for each 50 ml, and a total of twelve liquids are divided. The TMAC concentration was measured by ion chromatography using these different liquids. The metal ion concentration was measured by ICP mass spectrometry, and the pH was measured by a pH meter. The results are shown in Table 3, respectively. It can be seen from Table 3 that when the pH becomes 7 or less, the metal ion concentration will rise 〇 [0083] 〔 [Table 3] S liquid 馥 pH conductivity (»S / cm) TMAC concentration (mol / 1) HC1 concentration (mol / 1) gold ion concentration (ppb> Na A! K Ca Cr Fe Ni Cu A 9.0 0 0 0 &lt; 2, 5 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt;;2.5&lt;0.3 B 8.8 0 0 0 &lt;2.5 &lt; 1.0 1.8 &lt; 5.0 &lt;0.5 &lt;4.0 &lt; 2.5 &lt; 0.3 C 8,8 22 0.25 0 &lt;2.5 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt; 0.5 &lt; 4.0 &lt;2.5 &lt;0.3 D 8.9 76 1.17 0 &lt; 2.5 &lt; 1.0 &lt;1.0 &lt; 5.0 &lt; 0.5 &lt;4.0 &lt;2.5 &lt;0.3 &lt; 0.3 E 8.8 94 1.64 0 &lt;2.5 8.3 &lt; 1.0 &lt; 5.0 &lt; 0.5 14.5 &lt;2.5 &lt;0.3 F-1 8.9 96 1.69 0 &lt; 2.5 21.5 &lt;1.0 &lt; 5.0 &lt; 0.5 30.5 &lt;2.5 &lt;0.3 F-2 0.? 220 1.55 0.36 &lt; 2.5 44.3 8.4 &lt; 5.0 &lt; 0.5 20.3 &lt; 2.5 &lt; 0.3 F-3 0.3 516 1.19 1.50 433.6 132.5 34.1 318.5 &lt; 0.5 75,1 2.5 0.8 F-4 0.2 731 0.53 2.91 1121.8 168.4 75.4 1765.5 &lt;0.5 198.5 3.5 1.6 F-5 0.1 762 0.22 3.58 654.3 470.5 25.2 1580.6 &lt;0.5 140,6 3.2 1.5 G 0.1 771 O.iO 3.89 184.7 62.8 8.6 274.3 &lt;0.5 75.1 2.4 0.5 Η 0.1 775 0.01 3.98 42.5 30.1 6.5 70.2 &lt; 0.5 21.1 1.8 0.3 [0084] Example 4 1001 Part No. A0101 Page 23 of 33 10质量为下下溶液。 The sulphate was condensed by the TMAC obtained by the method of Example i to adjust the 27. 5 mass and the prison solution. The resulting concentrated tmac solution was subjected to electrolysis engineering to produce TAAH. [0085] In the electrolysis process, a three-chamber electrolysis in which an anion exchange membrane and a cation exchange membrane (any exchange membrane are NAFION 90209 (made by DuPont)) are sequentially disposed from the anode. groove. The effective membrane area of the above-mentioned ion-parent replacement film is set to 2 dm 2 , and the Nafic film is provided with the side having a few acid groups toward the cathode side. Platinum is used as the anode on the titanium plate, and SUS316 is used as the cathode. Circulating the sulfuric acid specified in 〇.5 in the anode chamber of the electrolytic cell; circulating the vaporized TMA solution between the anion exchange membrane and the cation exchange membrane on the cathode side; and circulating pure water in the cathode chamber to maintain the current density At 18 A/dm2, the temperature was maintained at 40 ° C while 'electrolysis was continuously performed. In the continuous operation, the concentration of tetramethylammonium hydroxide in the cathode chamber was set to 18% by mass. Similarly, the concentration of the liquid circulating in each chamber is set to a constant value, pure water is added when the concentration becomes rich, and the components contained therein are added when the concentration becomes light. [0086] After the start of electrolysis, the analysis results of the TAAH solution obtained after the operation state entered the stable 12 hours (safety) and at the time when the continuous operation was performed for 3 months are shown in Table 4, respectively. Example 5 The TMAC obtained by the method of Example 2 was electrolyzed in the same manner as in Example 4 to produce TMAH. The results are shown in Table 4. [Table 4] 10014667#^'^ A〇101 Page 24/ Total 33 1013093883-0 201228729 - Example 4 Example 5 After continuous operation after continuous operation, Na 1.5 1.1 2.0 1.3 AI 0 -9 0.5 1.1 0.7 metal ion concentration (ppbw) K 1.5 0.8 1.2 0.8 Ca 1.2 0.7 1.4 0.9 Cr &lt; 0.5 &lt; 0.5 &lt; 0.5 &lt; 0.5 &lt; 0.5 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 Ni &lt; 2.5 &lt; 2.5 &lt; 2.5 &lt; 2.5 Cu &lt; 0.3 &lt; 0.3 &lt; 0.3 &lt; 0.3 &lt; 0.3 Ο --- [Example 6 (Regeneration treatment of cation exchange resin (Η-type cation exchange resin)) The exchange resin 1 OOOial is filled into a PVC column with a diameter of 50 mm x 2000 mm. The space velocity SV at the time of passing through the ultrapure water and 1N-HC1 is set to 4 (1/time), except for the use of each liquid. The amount of liquid was changed to 5 L/L-resin, and the regeneration treatment was carried out in the same manner as in Example 1. &lt;Adsorption Engineering of TAA Ion&gt; A 5% mass% TMAH waste liquid having the same composition as that of Example 1 was passed through at a space velocity of SV = 20 (1/time). <Cleaning Process> Subsequently, 0.5 mass% TMAH of 21 was passed through at a space velocity SV = 5 (1/time) to wash the impedance component. <Contact Engineering with Hydrochloric Acid/Recycling Engineering of TAAC> Next, 8000 ml of 1N-HC1 was used as an eluent at a space velocity "= 10014667^, single number A0101, page 25/33, 1013093883-0, 201228729 5 (1) / time) to carry out the liquid, so that the adsorbed τ ΜΑ ion forms TMAC and then dissolves. The eluate is separately obtained in order, and can be divided into twenty-three liquids as shown below. First, distinguish 〇~1 000 ml (distinguish liquid A) From 1〇〇〇 to 5000ml, every 5〇〇mi is divided into 8 types (different from liquid B~ Π '5000 to 600 〇ml, then 1 〇〇ml is divided and 1 分 is divided. (Different liquids J-1 to J-10) and 6000 to 8000 ml are divided into four types (dividing liquids K to N) for every 500 ml, and are divided into twenty-two kinds of liquids. The TMAC concentration was measured by chromatography, and the metal ion concentration was measured by ICP mass spectrometry to measure the pH by a Qiu measuring device. The results are shown in Table 5, Figure 4, and Figure 5. In addition, the liquid B to j_5 will be distinguished. The pH, conductivity, TMAC concentration, and metal ion concentration of the total liquid are shown in Table 6. [Table 5] [Page 5] Page 26 of 33 10014667^Single Number 1013093883-0 201228729 [Table 6] Total Liquid pH Conductivity of BJ-5 TMAC HC1 Na A1 K Ca Cr Fe Ni Cn ( mS / cm) (mol / l) (mol / 1) ppb ppb ppb ppb ppb ppb ppb Total 8.7 53 0.71 0.00 3.5 3.5 &lt; 1.0 &lt; 5.0 &lt; 0.5 7.1 &lt; 2.5 &lt; 0.3 (7.7 wt%)

As can be seen from Table 5, it is known that the concentration of metal ions increases from j_6 which becomes 7 or less. In addition, from the results of Table 6, it can be seen that the concentration of the metal ions of the liquids of the liquids 8 to 5 is 3 5 ppb or less, and the TMAC concentration is 7.7 mass!; (; (〇71m〇1/ 1), and the TMAC recovery rate was 87.8%.

[Simple diagram of the figure J Form nickname 100146674 Distinguish liquid 逋 pH t conductance (mS / cm) TMAC concentration (mol /1) HC1 concentration (mol /1) Full genus. Sub-degree (PPbw) Ka A1 K Ca Cr Fe Ni Cu A 9.1 0 0 0 2.7 9.3 &lt; 1.0 &lt;5.0 &lt;0.5 &lt; 4.0 &lt;2.5 &lt;0.3 B 8.9 20 0.23 0 6.5 3.5 &lt; 1.0 &lt;5.0 &lt;0.5 &lt;4.0 &lt; 2.5 &lt;0.3 C 8.9 52 0.69 0 10.2 &lt; 1.0 1.5 &lt;5.0 &lt;0.5 &lt;4.0 &lt;2.5 &lt;2.5 &lt;0.3 D 8.9 56 0.75 0 3.3 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt;0.5 &lt;&lt; 2.5 &lt;0.3 E 8.8 57 0.77 0 2.1 &lt; 1,0 &lt; IG &lt; 5.0 &lt;0.5 &lt;4.0 &lt;2.5 &lt;0.3 F 8.8 57 0.77 0 2.8 &lt; 1.0 &lt; io &lt; 5 .0 &lt;0.5 &lt; 4.0 &lt; 2.5 &lt; 0.3 G 8.8 57 0.77 0 1.9 &lt; 1.0 &lt; 1.0 &lt; 5.0 &lt;0.5 4.6 &lt;2.5 &lt; 0.3 Η 8.7 5S 0.79 0 0.8 &lt; 1.0 &lt; 1.0 &lt;5.0 &lt;0.5 6.6 &lt;2.5 &lt;0.3 I 8.6 58 0.79 0 2.2 8.3 &lt; 1.0 &lt;5.0 &lt;0.5 19.3 &lt;2.5 &lt; 0 3 Jl 8.6 58 0.79 0 1.2 13.5 &lt; 1.0 &lt; 5.0 &lt; 0.5 24.1 &lt; 2.5 &lt; 0.3 J-2 8.6 58 0.79 0 1.8 22 &lt; 1,0 &lt;5.0 &lt;0.5 30-7 &lt;2.5 &lt;0.3 J-3 8.6 58 0.79 0 1.6 18.9 &lt; Io &lt; 5.0 &lt; 0.5 34.2 &lt;2.5 &lt;0.3 &lt;0.3 J-4 8.5 58 0.79 0 1.9 20.4 6.4 &lt;5.0 &lt; 0.5 35-7 &lt; 2.5 &lt; 0.3 J-5 8.5 58 0-79 0 3.6 24.2 11.2 28 &lt;0.5 42.9 &lt; 2-5 0.6 3-6 6.1 71 0.79 0 243-3 103.3 38.4 230.1 &lt;0.5 86-5 &lt; 2.5 0.9 J-7 2.4 83 0.78 0.02 670.7 201.4 65.5 880.4 &lt;0.5 122.6 3.4 2.2 JS 1.1 98 0.76 0.05 1333.6 245.5 92.3 1847.8 &lt;0.5 179.1 6.4- 1.5 J-9 0.7 131 0 64 0.20 1242 231.5 77.1 2204.1 &lt;0.5 164.1 6.2 1.6 ΜΌ 0.5 183 0.45 0.30 459.2 216.5 1S.1 1287.4 &lt; 0.5 134 5.9 l K 0.4 264 Ο.Ϊ5 0.71 218.4 87 6.8 542 &lt; 0.5 86.6 2.8 0.7 L 0.4 315 0.04 0.91 53.5 46.2 3.6 142.2 &lt;0.5 74.6 &lt; 2.5 &lt; 0.3 M 0.3 322 0.01 0.98 34.4 32.8 3.1 70.4 &lt; 0.5 48.8 &lt; 2.5 &lt; 0.3 N 0.3 337 0 1.01 Π.6 9.2 1.7 14.8 &lt; 0.5 26.9 &lt; 2.5 &lt; 0.3 [0095] 1 is a schematic view showing an embodiment of a manufacturing apparatus A0101 of the method for producing a four-sinter-base salt of the present invention, page 33 of 101309388Σ 201228729. Figure 2 is a graph relating to an embodiment of the invention. Figure 3 is a graph relating to an embodiment of the invention. Figure 4 is a graph relating to an embodiment of the invention. Figure 5 is a graph relating to an embodiment of the invention. [Main component symbol description] [0096]No | 丽棚#料号纽01 1013093883-0 Page 28 of 33

Claims (1)

201228729 VII. Patent application scope: 1. A method for producing a tetraalkylammonium salt solution, which is a solution containing a metal ion and a tetraalkylammonium hydroxide to obtain a solution containing a tetraalkylammonium salt. The method comprises the following steps: (1) passing a solution containing a metal ion and a tetraalkylammonium hydroxide into an adsorption tower filled with a hydrogen ion-type cation exchange resin, so that the tetraalkylammonium ion in the solution is adsorbed in the cation exchange An adsorption process on the resin; and (2) in the adsorption process, an acid solution is introduced into the adsorption column filled with a cation exchange resin adsorbed with tetradecane' ammonium ion to adsorb the cation exchange resin Dissolving the tetraalkylammonium ion into the acid salt, and recovering the first-class liquid discharged from the adsorption tower to a recovery project of a storage tank; and, in the recycling process, measuring the outflow from the adsorption tower At least one of pH and electrical conductivity of the liquid, when the pH of the effluent reaches a predetermined pH, and the point at which the electrical conductivity changes only by a predetermined amount of change in electrical conductivity When one of the effluent to stop toward the retention groove recovered. The method for producing a tetraalkylammonium salt solution according to claim 1, wherein in the recycling process, the acid solution is a strong acid, and the effluent toward the storage tank is recovered. The predetermined pH of the effluent that is stopped is in the range of 3 to 8. 3. The method for producing a tetraalkylammonium salt solution according to claim 1, wherein in the recovery process, the time at which the tetraalkylammonium salt flows out in a state in which the concentration is maintained in a certain state The electrical conductivity of the predetermined electrical conductivity of the effluent that stops the recovery of the effluent toward the storage tank is 10014667#单麟鹿01 Page 29/33 pages 1013093883-0 201228729 %. A method for producing a tetraalkylammonium hydroxide, which comprises: after the tetraalkylammonium salt is produced by the method according to any one of claims 1 to 3, the obtained four The use of an alkylammonium salt as a raw material to produce tetraalkylammonium hydroxide. a manufacturing apparatus for producing a tetraalkylammonium salt solution from a tetraalkylammonium hydroxide solution, and comprising: an adsorption tower filled with a cation exchange resin; and recovering one flowing out from the adsorption tower a reservoir of the effluent; and a pH measuring element for measuring the pH of the effluent and at least one of a conductivity measuring element for measuring the electrical conductivity of the effluent. 1001466#单号谢01 Page 30 of 33 1013093883-0