TW202317662A - Method for refining acidic solution - Google Patents

Method for refining acidic solution Download PDF

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TW202317662A
TW202317662A TW111132827A TW111132827A TW202317662A TW 202317662 A TW202317662 A TW 202317662A TW 111132827 A TW111132827 A TW 111132827A TW 111132827 A TW111132827 A TW 111132827A TW 202317662 A TW202317662 A TW 202317662A
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exchange resin
ion exchange
refining
acidic solution
solution
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高田智子
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日商奧璐佳瑙股份有限公司
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/07—Processes using organic exchangers in the weakly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/10—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds
    • B01J49/16—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds containing cationic and anionic exchangers in separate beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/10—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds
    • B01J49/18—Regeneration or reactivation of ion-exchangers; Apparatus therefor of moving beds of mixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/60—Cleaning or rinsing ion-exchange beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Engineering & Computer Science (AREA)
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  • Treatment Of Water By Ion Exchange (AREA)
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Abstract

An object of the invention is to provide a refining method that is capable of providing an acidic solution with a reduced concentration of impurities. Specifically, the invention provides a method for refining an acidic solution that uses a refined ion exchange resin obtained by bringing an ion exchange resin that represents the refinement target into contact with a mineral acid solution having a metal impurity content of not more than 1 mg/L and a concentration of at least 5% by weight, wherein the total amount of metal impurities eluted when a hydrochloric acid solution with a concentration of 3% by weight is passed through the refined ion exchange resin at a 25* volume ratio is 5 [mu]g/mL-R or less. It is preferable that the content of each of sodium (Na), calcium (Ca), magnesium (Mg) and iron (Fe) in the mineral acid solution does not exceed 200 [mu]g/L, and that the ion exchange resin contains a styrene type strongly acidic ion exchange resin having a particle size of at least 100 [mu]m but not more than 400 [mu]m.

Description

酸性溶液之精製方法Refining method of acidic solution

本申請案係基於2021年10月14日申請之日本申請案即日本特願2021-168956，並且基於該申請案主張優先權。該申請案的全部內容藉由引用而納入本申請案。 本發明係關於酸性溶液之精製方法，詳細而言係關於使用了離子交換樹脂之將酸性溶液中的金屬雜質減少之精製方法。 This application is based on Japanese Patent Application No. 2021-168956 filed on October 14, 2021, and priority is claimed based on this application. The entire content of this application is incorporated into this application by reference. The present invention relates to a purification method of an acidic solution, and specifically relates to a purification method for reducing metal impurities in an acidic solution using an ion exchange resin.

在半導體製造步驟中，在各種步驟中分別使用適合的藥水，但一律要求低雜質濃度。 無機酸、有機酸般的酸性溶液亦為在半導體製造步驟中使用之藥水，並且要求低雜質濃度。 作為酸性溶液之精製方法，近年來已有人報告藉由使用設備費用負擔小、節約能源且可高度地精製去除雜質之離子交換樹脂、離子交換過濾器等之離子交換法所為之精製方法。 In semiconductor manufacturing steps, appropriate chemicals are used in various steps, but low impurity concentrations are uniformly required. Acidic solutions like inorganic acids and organic acids are also used in semiconductor manufacturing steps, and require low impurity concentrations. As a purification method of acidic solution, in recent years, there have been reports of purification methods using ion exchange resins, ion exchange filters, etc., which are less burdensome in equipment costs, save energy, and can be highly purified to remove impurities.

例如關於使用陰離子交換樹脂、陽離子交換樹脂之酸溶液之精製，存在各種先前技術。螯合樹脂亦普遍使用於酸性溶液之精製，尤其普遍使用於有價物回收，並且存在大量的文獻。 就酸性溶液之精製而言，存在關於從無機酸、有機酸、或者有機溶媒與有機酸之混合溶液去除金屬之文獻。 就無機酸之精製而言，已知尤其在鹽酸中各種金屬以氯化物錯合物的形式存在，可利用陰離子樹脂來去除(例如參照日本特開2020-1955號公報、日本特許4523321號公報及DIAION：DIAION離子交換樹脂・合成吸附劑手冊[II]、三菱化成工業(股)、P95-97、第87-89圖)。例如在日本特開2020-1955號公報中，將微粒子過濾器、陰離子交換樹脂及陽離子交換樹脂使用於包含金屬錯合物之粗鹽酸之精製。又亦存在關於磷酸中的金屬去除方法之報告(例如參照日本特開2016-22477號公報)。 關於有機酸之精製，亦有人在過去的文獻中報告可使用陰離子樹脂而去除金屬雜質，並且報告以成為精製對象的有機酸型使用之情形(例如參照日本特許4534591號公報)和以Cl型使用之情形(例如日本特開昭61-274789號公報)等。 在日本特許6772132號公報中，使用非金屬型的樹脂(H型、OH型)而從有機酸與有機溶媒之混合物減少金屬雜質。 又在有機酸之製造時，有進行藉由離子交換樹脂之處理之情形。例如日本特許3965220號公報報告了下列方法：以藉由離子交換膜所為之電透析、螯合樹脂處理、藉由離子交換膜所為之水解電透析來處理以利用微生物所為之發酵法獲得之粗有機酸鹽溶液，從而製造有機酸。 For example, there are various prior arts regarding purification of acid solutions using anion exchange resins and cation exchange resins. Chelating resins are also commonly used in the purification of acidic solutions, especially in the recovery of valuables, and there are a large number of documents. As far as the purification of acidic solutions is concerned, there are literatures on the removal of metals from inorganic acids, organic acids, or mixed solutions of organic solvents and organic acids. As far as the purification of inorganic acids is concerned, it is known that various metals exist in the form of chloride complexes in hydrochloric acid, which can be removed by anion resins (for example, refer to Japanese Patent Laid-Open No. 2020-1955, Japanese Patent No. 4523321 and DIAION: DIAION Ion Exchange Resin and Synthetic Adsorbent Handbook [II], Mitsubishi Chemical Industry Co., Ltd., P95-97, Figures 87-89). For example, in Japanese Unexamined Patent Publication No. 2020-1955, a fine particle filter, anion exchange resin, and cation exchange resin are used for purification of crude hydrochloric acid containing metal complexes. There is also a report on a metal removal method in phosphoric acid (for example, refer to JP-A-2016-22477). Regarding the purification of organic acids, it has also been reported in past literature that anionic resins can be used to remove metal impurities, and reports have been made on the use of organic acids as the object of purification (for example, refer to Japanese Patent No. 4534591) and Cl-form use. The situation (for example, Japanese Patent Application Laid-Open No. 61-274789 ) and the like. In Japanese Patent No. 6772132, metal impurities are reduced from a mixture of an organic acid and an organic solvent by using a non-metallic resin (H type, OH type). Also, in the manufacture of organic acids, treatment with ion exchange resins may be performed. For example, Japanese Patent No. 3965220 has reported the following methods: treating crude organic matter obtained by fermentation by microorganisms through electrodialysis by ion-exchange membranes, chelating resin treatment, and hydrolysis electrodialysis by ion-exchange membranes. Acid solution to produce organic acid.

伴隨電子設備之小型化所致之高積體化，期望半導體製造步驟所使用之酸性溶液之雜質亦進一步減少。 因此，本發明之目的係提供可提供雜質濃度進一步減少之酸性溶液之精製方法。 Accompanied by the miniaturization of electronic equipment resulting in high integration, it is expected that the impurities in the acidic solution used in the semiconductor manufacturing process will be further reduced. Therefore, it is an object of the present invention to provide a refining method that can provide an acidic solution with a further reduced impurity concentration.

藉由離子交換樹脂之精製對象即酸性溶液，存在易於使金屬雜質從離子交換樹脂溶出之中性溶液中不會發生的酸溶液中特有的課題。 因此，本案發明人發現減少酸性溶液精製時金屬雜質從離子交換樹脂溶出之方法，藉由使用金屬雜質之溶出減少之離子交換樹脂，達成上述目的。 具體而言，上述目的係藉由下述[1]至[8]而達成。 [1]一種酸性溶液之精製方法，係使用離子交換樹脂之酸性溶液之精製方法，其特徵為： 前述離子交換樹脂係藉由使金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸精製對象的離子交換樹脂而進行精製從而得到的精製離子交換樹脂，且在使濃度3重量%的鹽酸以體積比25倍量通過前述精製離子交換樹脂時溶出之總金屬雜質溶出量為5μg/mL-R以下。 [2]如前述[1]之酸溶液之精製方法，其中前述礦酸溶液中的鈉(Na)、鈣(Ca)、鎂(Mg)、及鐵(Fe)之含量分別為200μg/L以下。 [3]如前述[1]或[2]之酸溶液之精製方法，其中前述離子交換樹脂包含苯乙烯型強酸性離子交換樹脂。 [4]如前述[3]之酸溶液之精製方法，其中前述苯乙烯型強酸性離子交換樹脂之粒徑為100μm以上且400μm以下。 [5]一種酸溶液精製用離子交換樹脂之再生方法，其特徵為使使用如前述[1]~[4]中任1項之精製方法而將酸溶液精製後的離子交換樹脂接觸礦酸溶液後，實施水洗淨直到洗淨水之TOC達30ppb以下。 [6]如前述[1]~[4]中任1項之酸性溶液之精製方法，其中使用藉由如前述[5]之再生方法而再生之再生離子交換樹脂作為前述離子交換樹脂。 [7]一種酸性溶液精製裝置，其特徵為具備離子交換樹脂精製手段、與酸性溶液精製手段，其中 該離子交換樹脂精製手段係藉由使金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸對象的離子交換樹脂而進行精製從而得到精製陽離子交換樹脂，且在使濃度3重量%的鹽酸以體積比25倍量通過前述精製離子交換樹脂時溶出之總金屬雜質溶出量為5μg/mL-R以下， 該酸性溶液精製手段係使用前述精製離子交換樹脂而將酸性溶液精製。 [8]如前述[7]之酸溶液精製裝置，其具有酸性溶液之精製後的離子交換樹脂之再生功能。 Due to the acidic solution that is the object of purification of the ion exchange resin, there is a unique problem in the acid solution that tends to elute metal impurities from the ion exchange resin, which does not occur in a neutral solution. Therefore, the inventors of the present invention have found a method to reduce the elution of metal impurities from ion exchange resins during the purification of acidic solutions. By using ion exchange resins with reduced elution of metal impurities, the above object can be achieved. Specifically, the above objects are achieved by the following [1] to [8]. [1] A method for refining an acidic solution, which is a method for refining an acidic solution using an ion exchange resin, characterized in that: The aforementioned ion exchange resin is a refined ion exchange resin obtained by refining a mineral acid solution having a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more in contact with the ion exchange resin to be purified. When weight % hydrochloric acid passes through the aforementioned purified ion exchange resin in an amount 25 times the volume ratio, the amount of total metal impurities dissolved is 5 μg/mL-R or less. [2] The method for refining an acid solution according to the aforementioned [1], wherein the content of sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe) in the aforementioned mineral acid solution is 200 μg/L or less, respectively . [3] The method for purifying an acid solution according to [1] or [2] above, wherein the ion exchange resin includes a styrene-type strongly acidic ion exchange resin. [4] The method for purifying an acid solution according to [3] above, wherein the particle size of the styrene-type strongly acidic ion exchange resin is 100 μm or more and 400 μm or less. [5] A method for regenerating an ion-exchange resin for refining an acid solution, which is characterized in that the ion-exchange resin after refining the acid solution is contacted with a mineral acid solution using the refining method of any one of the aforementioned [1] to [4]. Afterwards, wash with water until the TOC of the washing water is below 30 ppb. [6] The method for purifying an acidic solution according to any one of [1] to [4] above, wherein a regenerated ion exchange resin regenerated by the regeneration method according to [5] above is used as the ion exchange resin. [7] An acidic solution refining device, characterized in that it is equipped with ion exchange resin refining means and acidic solution refining means, wherein The ion exchange resin purification means is to obtain a purified cation exchange resin by contacting a mineral acid solution with a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more with the ion exchange resin of the object, and making the concentration 3 The total metal impurity dissolution amount that dissolves when the hydrochloric acid of weight % passes through aforementioned refining ion-exchange resin with volume ratio 25 times amount is below 5 μ g/mL-R, The means for purifying the acidic solution is to purify the acidic solution using the aforementioned purified ion exchange resin. [8] The acid solution refining device according to the aforementioned [7], which has a function of regenerating the ion exchange resin after refining the acid solution.

依照本發明，可提供能提供雜質濃度進一步減少之酸性溶液之精製方法。According to the present invention, a refining method capable of providing an acidic solution with a further reduced concentration of impurities can be provided.

上述及其它本申請案之目的、特徵、及優點，可藉由參照了例示本申請案之附圖的下述詳細說明而明瞭。The above and other objects, features, and advantages of the present application will be clarified by the following detailed description with reference to the accompanying drawings illustrating the present application.

以下詳細說明本發明之實施形態。本實施形態係實施本發明之一例，本發明並未限定於本實施形態。Embodiments of the present invention will be described in detail below. This embodiment is an example of implementing the present invention, and the present invention is not limited to this embodiment.

＜酸性溶液之精製方法＞ 本發明之酸性溶液之精製方法係使用預先接觸特定的礦酸溶液而精製之離子交換樹脂而將酸性溶液精製。 成為精製之對象的酸性溶液可將有機酸、或者無機酸(礦酸)之任一者設為對象。 作為有機酸，例如可列舉：檸檬酸、草酸、琥珀酸、酒石酸、乳酸、丙二酸、甲酸等。 作為礦酸，例如可列舉：鹽酸、硫酸、硝酸、磷酸等。 ＜Refining method of acidic solution＞ The purification method of the acidic solution of the present invention is to use the ion exchange resin purified by contacting a specific mineral acid solution in advance to refine the acidic solution. The acidic solution to be purified may be any one of organic acid or inorganic acid (mineral acid). Examples of organic acids include citric acid, oxalic acid, succinic acid, tartaric acid, lactic acid, malonic acid, and formic acid. As mineral acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. are mentioned, for example.

本案發明人為了減少酸性溶液精製時金屬雜質從離子交換樹脂溶出，探討了使在使用於酸性溶液之精製前的離子交換樹脂(以下亦稱為「精製對象的離子交換樹脂」)接觸礦酸溶液而精製，但若接觸之礦酸溶液本身包含金屬雜質，則不但無法減少離子交換樹脂內的金屬雜質，反而會有使礦酸水溶液中的金屬雜質吸附於離子交換樹脂而使其增大之情形。因此，可預料藉由將接觸礦酸溶液後的離子交換樹脂使用於酸性溶液之精製，反而會使大量的金屬物質等在酸性溶液中溶出。尤其已知金屬之中又以鈉(Na)、鈣(Ca)、鎂(Mg)、鐵(Fe)係相較於其它金屬而言在離子交換樹脂內的含量多，即使藉由接觸礦酸溶液亦難以減少含量。 因此，將在使濃度3重量%的鹽酸以體積比25倍量通過藉由使含有金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸精製對象的離子交換樹脂而得到的精製離子交換樹脂時溶出之總金屬雜質量設為5g/mL-R以下，並將該離子交換樹脂使用於酸性溶液之精製，藉此減少酸性溶液精製時金屬雜質從離子交換樹脂溶出，可提供雜質濃度進一步減少之酸性溶液。 In order to reduce the elution of metal impurities from the ion-exchange resin during the purification of the acidic solution, the inventors of the present invention have studied the contact of the ion-exchange resin (hereinafter also referred to as "the ion-exchange resin to be purified") before the purification of the acidic solution with the mineral acid solution. And refining, but if the mineral acid solution itself contains metal impurities, it will not only fail to reduce the metal impurities in the ion exchange resin, but will cause the metal impurities in the mineral acid aqueous solution to be adsorbed on the ion exchange resin to increase it. . Therefore, it is expected that by using the ion exchange resin contacted with the mineral acid solution for the purification of the acid solution, a large amount of metal substances etc. will be eluted in the acid solution. In particular, it is known that among metals, sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe) are more contained in ion exchange resins than other metals. It is also difficult to reduce the content of the solution. Therefore, the hydrochloric acid with a concentration of 3% by weight is obtained by contacting a mineral acid solution containing a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more with the ion exchange resin to be purified at a volume ratio of 25 times. The total amount of metal impurities dissolved during the refined ion exchange resin is set to be below 5g/mL-R, and the ion exchange resin is used in the purification of acidic solution, thereby reducing the dissolution of metal impurities from the ion exchange resin during the purification of acidic solution. Provides an acidic solution with a further reduced concentration of impurities.

作為精製對象的離子交換樹脂，可使用陽離子交換樹脂及陰離子交換樹脂之任一者，又亦可將陽離子交換樹脂與陰離子交換樹脂組合而使用。 作為陽離子樹脂，可列舉：強酸性陽離子交換樹脂(SAC)、弱酸性陽離子交換樹脂(WAC)、及螯合樹脂等。 As the ion exchange resin to be purified, any one of a cation exchange resin and an anion exchange resin can be used, and a combination of a cation exchange resin and an anion exchange resin can also be used. Examples of the cation resin include strongly acidic cation exchange resins (SAC), weakly acidic cation exchange resins (WAC), and chelate resins.

作為強酸性陽離子交換樹脂，可使用具有磺酸基等官能基者，例如可使用：AMBERLITE(註冊商標)IR124(官能基：磺酸基)(DuPont公司製)、AMBERLITE(註冊商標)200CT(官能基：磺酸基)(DuPont公司製)、AMBERLITE IRN97H(官能基：磺酸基)(DuPont公司製)、ORLITE(註冊商標)DS-1(商品名、ORGANO(股)製)(官能基：磺酸基)、ORLITE(註冊商標)DS-4(商品名、ORGANO(股)製)(官能基：磺酸基)等。As the strongly acidic cation exchange resin, those having functional groups such as sulfonic acid groups can be used. For example, AMBERLITE (registered trademark) IR124 (functional group: sulfonic acid group) (manufactured by DuPont), AMBERLITE (registered trademark) 200CT (functional Group: sulfonic acid group) (manufactured by DuPont Corporation), AMBERLITE IRN97H (functional group: sulfonic acid group) (manufactured by DuPont Corporation), ORLITE (registered trademark) DS-1 (trade name, manufactured by ORGANO Co., Ltd.) (functional group: sulfonic acid group), ORLITE (registered trademark) DS-4 (trade name, manufactured by ORGANO Co., Ltd.) (functional group: sulfonic acid group), etc.

作為弱酸性陽離子交換樹脂，可使用具有羧基等官能基者，例如可使用：AMBERLITE(註冊商標)IRC76(官能基：羧酸基)(DuPont公司製)、AMBERLITE(註冊商標)FPC3500(官能基：羧酸基)(DuPont公司製)等。As the weakly acidic cation exchange resin, those having functional groups such as carboxyl groups can be used. For example, AMBERLITE (registered trademark) IRC76 (functional group: carboxylic acid group) (manufactured by DuPont), AMBERLITE (registered trademark) FPC3500 (functional group: carboxylic acid group) (manufactured by DuPont), etc.

螯合樹脂係具有可與金屬離子形成螯合物(錯合物)之官能基之樹脂。作為該官能基，只要是可與金屬離子形成螯合物(錯合物)之官能基即可，並未特別限制，但例如可列舉：胺基甲基磷酸基、亞胺基二乙酸基、硫醇基、多胺基等。作為螯合樹脂，從對於多個金屬種類之選擇性等的觀點來看，亦可具有胺基甲基磷酸基或亞胺基二乙酸基作為螯合基。Chelating resins are resins with functional groups that can form chelates (complexes) with metal ions. The functional group is not particularly limited as long as it is a functional group capable of forming a chelate (complex) with a metal ion, but examples include aminomethylphosphonic acid, iminodiacetoxy, Thiol group, polyamine group, etc. The chelate resin may have an aminomethyl phosphoric acid group or an iminodiacetate group as a chelate group from the viewpoint of selectivity to a plurality of metal species.

作為螯合樹脂，例如可使用：AMBERSEP(註冊商標)IRC747UPS(螯合基：胺基甲基磷酸基)、AMBERSEP(註冊商標)1RC748(螯合基：亞胺基二乙酸基)(皆為DuPont公司製)等。除此之外，作為H型螯合樹脂，亦可使用：ORLITE(註冊商標)DS-21(商品名、ORGANO(股)製)(螯合基：胺基甲基磷酸基)、ORLITE(註冊商標)DS-22(商品名、ORGANO(股)製)(螯合基：亞胺基二乙酸基)。As chelating resin, for example, can use: AMBERSEP (registered trademark) IRC747UPS (chelating group: amino methyl phosphoric acid group), AMBERSEP (registered trademark) 1RC748 (chelating group: iminodiacetoxy group) (all DuPont company), etc. In addition, as H-type chelating resin, ORLITE (registered trademark) DS-21 (trade name, manufactured by ORGANO Co., Ltd.) (chelating group: aminomethylphosphoryl group), ORLITE (registered trademark) can also be used as H-type chelating resin. Trademark) DS-22 (trade name, manufactured by ORGANO Co., Ltd.) (chelate group: iminodiacetoxy group).

AMBERSEP(註冊商標)IRC747UPS、AMBERSEP(註冊商標)IRC748之離子型係Na型為基準，但因利用上述方法使其接觸礦酸溶液，從而離子型從Na型變換為H型。The ionic type of AMBERSEP (registered trademark) IRC747UPS and AMBERSEP (registered trademark) IRC748 is based on the Na type, but the ion type is changed from the Na type to the H type by using the above method to contact the mineral acid solution.

作為陰離子交換樹脂，可為強鹼性陰離子交換樹脂(SBA)，亦可為弱鹼性陰離子交換樹脂(WBA)，弱鹼性陰離子交換樹脂亦可為硼選擇性陰離子交換樹脂。 作為強鹼性陰離子交換樹脂，可列舉：ORLITE(註冊商標)DS-2(商品名、ORGANO(股)製)、ORLITE(註冊商標)DS-5(商品名、ORGANO(股)製)等。 又，作為弱鹼性陰離子交換樹脂，除了ORLITE(註冊商標)DS-62(商品名、ORGANO(股)製)以外，可列舉：在官能基具有還原葡糖胺基之硼選擇性陰離子交換樹脂即AMBERLITE(註冊商標)IRA743(DuPont公司製)。 此外，陰離子交換樹脂可為OH型的陰離子交換樹脂，亦可為酸型的陰離子交換樹脂，但理想地使用與精製對象相同的酸型。 The anion exchange resin may be strongly basic anion exchange resin (SBA) or weakly basic anion exchange resin (WBA), and the weakly basic anion exchange resin may also be boron selective anion exchange resin. Examples of the strongly basic anion exchange resin include ORLITE (registered trademark) DS-2 (trade name, manufactured by ORGANO Co., Ltd.), ORLITE (registered trademark) DS-5 (trade name, manufactured by ORGANO Co., Ltd.), and the like. In addition, as the weakly basic anion exchange resin, in addition to ORLITE (registered trademark) DS-62 (trade name, manufactured by ORGANO Co., Ltd.), boron-selective anion exchange resins having a reduced glucosamine group in the functional group can be mentioned. That is, AMBERLITE (registered trademark) IRA743 (manufactured by DuPont). In addition, the anion exchange resin may be an OH-type anion-exchange resin or an acid-type anion-exchange resin, but it is desirable to use the same acid type as that to be purified.

在酸性溶液之精製中，離子交換樹脂亦可將陽離子交換樹脂與陰離子交換樹脂組合而使用，作為這樣的組合，可列舉：陰離子交換樹脂-陽離子交換樹脂之順序的組合、陽離子交換樹脂-陰離子交換樹脂之順序的組合、陽離子交換樹脂或陰離子交換樹脂-陽離子交換樹脂及陰離子交換樹脂之混床之順序的組合、陽離子交換樹脂及陰離子交換樹脂之混床-陽離子交換樹脂或陰離子交換樹脂之順序的組合。 可將陰離子交換樹脂與陽離子交換樹脂以混床使用，亦可依照陰離子交換樹脂→陽離子交換樹脂之順序處理。使用在酸性溶液中易於離子交換的陰離子交換樹脂而先將陰離子成分去除後，使用陽離子交換樹脂而將陽離子成分去除係屬有效。若存在兩性離子時，先利用陰離子交換樹脂來減少的話，對於後段的陽離子交換樹脂之負荷會較為減輕。又，由於陽離子交換基會捕捉金屬雜質，因此陽離子交換樹脂亦可作為高純化器(polisher)而配置在後段。可使用螯合樹脂來取代陽離子交換樹脂，亦可在陰離子交換樹脂之後段將陽離子交換樹脂與螯合樹脂組合而使用。 又亦可不使用陰離子樹脂，將強酸性陽離子交換樹脂、弱酸性陽離子交換樹脂、及螯合樹脂之中2種以上組合使用。 此外，離子交換樹脂亦包含在使用於酸性溶液之精製後，實施後述的再生處理而得之再生離子交換樹脂。 陽離子交換樹脂、陰離子交換樹脂之母體例如可列舉：苯乙烯樹脂、丙烯酸樹脂等。 In the purification of the acidic solution, the ion exchange resin can also be used in combination of a cation exchange resin and an anion exchange resin. Examples of such a combination include: a combination of anion exchange resin-cation exchange resin, and a combination of cation exchange resin-anion exchange resin. Combination of sequence of resins, combination of sequence of cation exchange resin or anion exchange resin-mixed bed of cation exchange resin and anion exchange resin, combination of sequence of mixed bed of cation exchange resin and anion exchange resin-sequence of cation exchange resin or anion exchange resin combination. Anion exchange resin and cation exchange resin can be used in a mixed bed, and can also be treated in the order of anion exchange resin → cation exchange resin. It is effective to use an anion exchange resin that is easy to ion-exchange in an acidic solution to first remove anion components, and then use a cation exchange resin to remove cation components. If there are zwitterions, if the anion exchange resin is used to reduce them first, the load on the cation exchange resin in the later stage will be relatively lightened. In addition, since the cation exchange group captures metal impurities, the cation exchange resin can also be used as a high-purifier (polisher) and arranged in the rear stage. A chelate resin may be used instead of the cation exchange resin, or a cation exchange resin and a chelate resin may be used in combination after the anion exchange resin. Also, instead of using an anion resin, two or more of strongly acidic cation exchange resins, weakly acidic cation exchange resins, and chelate resins may be used in combination. In addition, ion-exchange resins also include regenerated ion-exchange resins obtained by performing regeneration treatment described later after being used in the purification of acidic solutions. Examples of precursors of cation exchange resins and anion exchange resins include styrene resins, acrylic resins, and the like.

此等離子交換樹脂之中，從多數的金屬雜質為陽離子性來看，使用強酸性離子交換樹脂為較佳，尤其從母體之強度高和清淨度的觀點來看，使用苯乙烯型強酸性離子交換樹脂為更佳。 強酸性離子交換樹脂若使用事先製備為H型者，則可藉由陽離子性雜質與離子交換基之H+交換而減少雜質，因H+之增加對於酸溶液之組成造成的影響小而為較佳。 此外，當酸性溶液為有機酸，並且使用陰離子交換樹脂作為離子交換樹脂時，使用丙烯酸系陰離子交換樹脂為較佳。 由於在有機酸中陰離子交換樹脂之離子型變換為酸型及金屬離子型，因此發生離子型之變換所致之膨潤收縮，若反覆通液與再生則有樹脂破碎之情形。從耐膨潤收縮性強且為具有柔軟性之母體，例如即使從OH型膨潤為有機酸型亦少破碎等的觀點來看，陰離子交換樹脂亦可包含耐膨潤收縮性強的丙烯酸樹脂而構成。又，藉由使用膨潤收縮大的丙烯酸系陰離子交換樹脂，易於檢測壓力變動。 Among these ion exchange resins, it is better to use a strong acid ion exchange resin from the point of view that most of the metal impurities are cationic. Resin is more preferable. If the strongly acidic ion exchange resin is prepared in H-type in advance, impurities can be reduced by H+ exchange between cationic impurities and ion-exchange groups. It is better because the increase of H+ has little effect on the composition of the acid solution. Furthermore, when the acidic solution is an organic acid, and an anion exchange resin is used as the ion exchange resin, it is preferable to use an acrylic anion exchange resin. Since the ion type of anion exchange resin in organic acid is converted into acid type and metal ion type, swelling and contraction caused by the conversion of ion type will occur, and the resin will be broken if the liquid is passed through and regenerated repeatedly. The anion exchange resin can also be composed of an acrylic resin with strong swelling and shrinking resistance from the viewpoint of being a flexible matrix with strong swelling and shrinking resistance, for example, even if the OH type swells into an organic acid type, it is less broken. In addition, by using an acrylic anion exchange resin with a large swelling and contraction, it is easy to detect pressure fluctuations.

離子交換樹脂係以使用調和平均徑為100μm以上且400μm以下者為較佳。若粒徑在該範圍，則因表面積變大且雜質離子變得易於接近官能基，金屬去除性變好而為較佳。又在後述的離子交換樹脂之再生中，亦因表面積大且再生藥水易於接近官能基而變得易於再生而為較佳。 此外，在本發明中，離子交換樹脂之平均粒徑係指使用雷射繞射式粒度分布計所測定之調和平均徑。 As the ion exchange resin, it is preferable to use one having a harmonic mean diameter of not less than 100 μm and not more than 400 μm. If the particle diameter is within this range, the surface area becomes large, and impurity ions tend to approach the functional group, thereby improving metal removability, which is preferable. In the regeneration of the ion exchange resin described later, it is also preferable because the surface area is large and the regeneration chemical is easy to approach the functional group, so that regeneration is easy. In addition, in this invention, the average particle diameter of an ion exchange resin means the harmonic average diameter measured using the laser diffraction particle size distribution meter.

又，離子交換樹脂係以使用除了平均粒徑在前述的範圍以外，交聯度(二乙烯苯含量)為2%以上且13%以下者為較佳。若交聯度在該範圍，則因樹脂內部之擴散性增加，進一步金屬去除性和離子交換樹脂之再生容易度增加而為較佳。Moreover, it is preferable to use the ion exchange resin whose average particle diameter is in the said range, and the degree of crosslinking (divinylbenzene content) is 2% or more and 13% or less. When the degree of crosslinking is within this range, it is preferable because the diffusivity inside the resin increases, and the easiness of metal removal and regeneration of the ion exchange resin increases.

從以上的觀點來看，作為離子交換樹脂，更宜使用下述強酸性陽離子交換樹脂：係事先製備為H型之強酸性陽離子樹脂，其中樹脂母體為苯乙烯，平均粒徑100μm以上且400μm以下，且交聯度(二乙烯苯含量)為2%以上且13%以下。From the above point of view, as the ion exchange resin, it is more appropriate to use the following strongly acidic cation exchange resin: it is a strong acidic cation resin prepared in advance as H type, wherein the resin matrix is styrene, and the average particle size is more than 100 μm and less than 400 μm , and the degree of crosslinking (divinylbenzene content) is 2% or more and 13% or less.

使用於離子交換樹脂之精製之礦酸溶液係無機酸之溶液。作為礦酸例如可列舉：鹽酸、硫酸、硝酸等。作為構成溶液之溶媒，例如：純水(比電阻：約10MQ・cm)、超純水(比電阻：約18MQ・cm)等水。The refined mineral acid solution used in the ion exchange resin is a solution of inorganic acid. As mineral acid, hydrochloric acid, sulfuric acid, nitric acid etc. are mentioned, for example. As the solvent constituting the solution, for example: water such as pure water (specific resistance: about 10MQ·cm), ultrapure water (specific resistance: about 18MQ·cm).

離子交換樹脂之精製所使用之礦酸溶液中的含有金屬雜質量為1mg/L以下，愈少愈好，可為0.5mg/L以下，亦可為0.2mg/L以下。當礦酸溶液中的含有金屬雜質量大於1mg/L時，無法得到充分的離子交換樹脂內的金屬雜質量減少效果。The amount of metal impurities contained in the mineral acid solution used for the purification of the ion exchange resin is less than 1 mg/L, the less the better, it can be less than 0.5 mg/L, and it can also be less than 0.2 mg/L. When the amount of metal impurities contained in the mineral acid solution exceeds 1 mg/L, a sufficient effect of reducing the amount of metal impurities in the ion exchange resin cannot be obtained.

礦酸溶液之礦酸濃度為5重量%以上，亦可為10重量%以上。當礦酸溶液之礦酸之濃度小於5重量%時，無法得到充分的離子交換樹脂內的金屬雜質量減少效果。礦酸溶液之礦酸之濃度之上限例如為37重量%。The mineral acid concentration of the mineral acid solution may be 5% by weight or more, and may be 10% by weight or more. When the concentration of the mineral acid in the mineral acid solution is less than 5% by weight, a sufficient effect of reducing the amount of metal impurities in the ion exchange resin cannot be obtained. The upper limit of the concentration of mineral acid in the mineral acid solution is, for example, 37% by weight.

在此金屬雜質係除了金屬以外亦包含金屬雜質離子之概念，作為代表性者，例如可列舉：鈉(Na)、鈣(Ca)、鎂(Mg)、及鐵(Fe)等。Here, the metal impurity is a concept including metal impurity ions in addition to metals, and typical examples include sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe).

離子交換樹脂之精製所使用之礦酸溶液中的鈉(Na)、鈣(Ca)、鎂(Mg)、及鐵(Fe)之各含量係愈少愈好，可分別為200μg/L以下，亦可分別為100μg/L以下。 藉由使此等金屬雜質含量少的礦酸溶液接觸陽離子交換樹脂，可確實且有效地使離子交換樹脂內的鈉(Na)、鈣(Ca)、鎂(Mg)、及鐵(Fe)等金屬雜質之含量減少。 The contents of sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe) in the mineral acid solution used in the purification of ion exchange resins should be as low as possible, and can be below 200 μg/L respectively. It can also be below 100μg/L respectively. By contacting the mineral acid solution with low metal impurity content with the cation exchange resin, sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe) in the ion exchange resin can be reliably and effectively The content of metal impurities is reduced.

在離子交換樹脂之精製中與離子交換樹脂接觸之礦酸溶液之溫度例如為0~40℃之範圍。The temperature of the mineral acid solution in contact with the ion exchange resin in the purification of the ion exchange resin is, for example, in the range of 0 to 40°C.

可將在使濃度3重量%的鹽酸以體積比25倍量通過藉由離子交換樹脂之精製所得之精製離子交換樹脂時溶出之總金屬雜質溶出量設為5μg/mL-R以下。總金屬雜質溶出量係愈少愈好，亦可為1μg/mL-R以下。藉由將該總金屬雜質溶出量設為5μg/mL-R以下，可減少當將該離子交換樹脂使用於酸性溶液之精製時，從離子交換樹脂溶出至酸性溶液中的此等金屬雜質之溶出量，其結果為可得到適合半導體製造步驟的雜質濃度更進一步減少之酸性溶液。The amount of total metallic impurities eluted when 3% by weight hydrochloric acid is passed through the purified ion exchange resin obtained by refining the ion exchange resin in an amount 25 times the volume ratio can be set to 5 μg/mL-R or less. The less dissolved amount of total metal impurities, the better, and it can also be below 1 μg/mL-R. By setting the amount of the total metal impurities eluted to 5 μg/mL-R or less, when the ion exchange resin is used in the purification of an acidic solution, the elution of these metal impurities from the ion exchange resin into the acidic solution can be reduced As a result, an acidic solution with a further reduced impurity concentration suitable for semiconductor manufacturing steps can be obtained.

溶出之金屬雜質亦可包含鈉(Na)、鈣(Ca)、鎂(Mg)、或鐵(Fe)之中至少任1個金屬。The eluted metal impurities may also contain at least one metal among sodium (Na), calcium (Ca), magnesium (Mg), or iron (Fe).

亦可在離子交換樹脂之精製之後，包含將經接觸礦酸溶液後得到的精製離子交換樹脂利用純水、超純水等洗淨水來洗淨之洗淨步驟。藉由在使精製離子交換樹脂接觸礦酸溶液後利用純水、超純水等洗淨水來洗淨，可在從精製離子交換樹脂去除礦酸溶液時，抑制金屬雜質之再汙染等。After purification of the ion exchange resin, a washing step of washing the purified ion exchange resin obtained by contacting the mineral acid solution with washing water such as pure water or ultrapure water may be included. After the purified ion exchange resin is brought into contact with the mineral acid solution, the purified ion exchange resin is washed with pure water, ultrapure water, or other washing water, so that recontamination of metal impurities can be suppressed when the mineral acid solution is removed from the purified ion exchange resin.

作為在洗淨步驟中與陽離子交換樹脂接觸之洗淨水，可列舉：純水、超純水等，從抑制精製後的汙染等的觀點來看，亦可為超純水。Examples of the washing water to be brought into contact with the cation exchange resin in the washing step include pure water, ultrapure water, and the like. From the viewpoint of suppressing contamination after purification, etc., ultrapure water may also be used.

在洗淨步驟中與陽離子交換樹脂接觸之洗淨水之溫度例如為1~80℃，15~30℃為較佳。The temperature of the washing water in contact with the cation exchange resin in the washing step is, for example, 1 to 80°C, preferably 15 to 30°C.

＜離子交換樹脂之再生＞ 本發明係使用藉由以上說明之步驟所得之精製離子交換樹脂而實施酸性溶液之精製者，但經使用於精製後之離子交換樹脂、尤其陽離子交換樹脂可在實施再生處理後，再度作為精製對象的離子交換樹脂而進行精製處理，並再度利用於酸性溶液之精製。 經使用於精製後之離子交換樹脂之再生係藉由下述而實施：使用鹽酸、硫酸等礦酸溶液而進行再生處理，藉由水洗淨而去除礦酸後，再度將對象酸溶液精製。礦酸濃度係以1當量以上的濃度為較佳。尤其本發明之離子交換樹脂係接觸金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液而精製，因此再生之情形亦期望使用相同的方法而再生。酸濃度和酸通液量只要根據再生之樹脂之在使金屬含量為濃度3重量%的鹽酸以體積比25倍量通過時溶出之總金屬雜質溶出量而適當決定即可。 此外，當使用陰離子交換樹脂作為離子交換樹脂時，由於在酸性溶液之精製過程中變換為礦酸型，因此未必需要利用前述方法來再生。亦可取而代之地利用1當量以上的濃度之氯化鈉溶液、和氫氧化鈉溶液、氫氧化四甲銨(TMAH)溶液來再生。亦可在再生後，變換為成為處理對象的酸或有機酸型而使用。此時使用之前述酸或有機酸係以金屬濃度比處理對象液更低為較佳。 ＜Regeneration of ion exchange resin＞ The present invention uses the refined ion exchange resin obtained through the steps described above to refine the acidic solution, but the ion exchange resin used for purification, especially the cation exchange resin, can be used as the object of purification again after regeneration treatment The ion exchange resin is refined and reused in the purification of acidic solution. The regeneration of the purified ion exchange resin is carried out by using a mineral acid solution such as hydrochloric acid or sulfuric acid to perform regeneration treatment, washing with water to remove the mineral acid, and refining the acid solution again. Mineral acid concentration is preferably more than 1 equivalent. In particular, the ion exchange resin of the present invention is purified by contacting a mineral acid solution with a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more. Therefore, it is desirable to use the same method for regeneration in the case of regeneration. The acid concentration and acid flow rate can be appropriately determined according to the amount of total metal impurities leached out when the regenerated resin is passed through 25 times the volume ratio of hydrochloric acid with a metal content of 3% by weight. In addition, when an anion exchange resin is used as the ion exchange resin, since it is converted into a mineral acid type during the purification process of the acidic solution, it is not necessarily necessary to regenerate it by the aforementioned method. Alternatively, a sodium chloride solution, a sodium hydroxide solution, and a tetramethylammonium hydroxide (TMAH) solution may be used for regeneration at a concentration of more than 1 N. After regeneration, it can also be used by switching to the acid or organic acid type to be treated. It is preferable that the aforementioned acid or organic acid used at this time has a metal concentration lower than that of the liquid to be treated.

當將經使用於有機酸精製後的離子交換樹脂再生時，為了確認有機酸是否殘留於再生後的離子交換樹脂，可藉由在使用前利用純水來洗淨離子交換樹脂，並確認洗淨水之總有機碳(TOC)未超過事先設定之值來判斷再生之優劣。不同於礦酸，有機酸可作為TOC而檢測出，因此可將殘留於樹脂之有機酸作為TOC而檢測並且作為樹脂之洗淨度之指標而適用於品質管理。When regenerating the ion exchange resin used for the purification of organic acids, in order to confirm whether the organic acid remains in the regenerated ion exchange resin, it is possible to wash the ion exchange resin with pure water before use, and confirm the cleaning. The total organic carbon (TOC) of water does not exceed the preset value to judge the quality of regeneration. Unlike mineral acids, organic acids can be detected as TOC, so the organic acids remaining in the resin can be detected as TOC and used as an indicator of the cleanliness of the resin for quality control.

亦可在本發明之精製方法中設置使用微粒子去除膜之步驟。例如若在精製過程之前段，即實施藉由離子交換樹脂之精製前的步驟中，設置使用微粒子去除膜之步驟，則可抑制酸性溶液中所包含之微粒子吸附於離子交換樹脂母體等汙染。又若在藉由離子交換樹脂之精製後的步驟中，設置使用微粒子去除膜之步驟，則不僅可減少酸性溶液中的溶出金屬雜質，亦可減少雜質微粒子。又若將使用微粒子去除膜之步驟設置於實施藉由離子交換樹脂之精製前及後的步驟，則可得到前述雙方的效果，可得到更進一步高純度的酸性溶液。A step of using a microparticle removal membrane may also be provided in the purification method of the present invention. For example, if a step of using a microparticle removal membrane is provided in the previous stage of the purification process, that is, before purification with ion exchange resins, it is possible to suppress contamination such as adsorption of microparticles contained in the acidic solution to the ion exchange resin matrix. In addition, if a step of using a particle removal membrane is provided in the step after purification by ion exchange resin, not only the eluted metal impurities in the acidic solution can be reduced, but also the impurity particles can be reduced. Also, if the step of using the microparticle removal membrane is arranged in the steps before and after the purification by ion exchange resin, the effects of both of the above can be obtained, and a further high-purity acidic solution can be obtained.

以上說明之本發明之精製方法係一種酸性溶液精製裝置，其特徵為具備離子交換樹脂精製手段、與酸性溶液精製手段，其中 該離子交換樹脂精製手段係藉由使金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸對象的離子交換樹脂而進行精製從而得到精製陽離子交換樹脂，且在使濃度3重量%的鹽酸以體積比25倍量通過前述精製離子交換樹脂時溶出之總金屬雜質溶出量為5μg/mL-R以下， 該酸性溶液精製手段係使用前述精製離子交換樹脂而將酸性溶液精製； 具體而言，具備離子交換樹脂管柱(第1管柱)作為藉由使含有金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸精製對象的離子交換樹脂而精製而得到精製離子交換樹脂之精製手段，且該第1管柱設置有用來供給用來將離子交換樹脂精製之礦酸之配管、用來將精製處理後的廢液排出之配管。 又，酸性溶液精製裝置具備離子交換樹脂管柱(第2管柱)作為進一步使藉由離子交換樹脂精製手段所得之精製離子交換樹脂接觸精製對象的處理液而精製之酸性溶液精製手段，且該第2管柱設置有用來供給精製對象的酸性溶液之配管、用來將精製處理後的酸性溶液排出之配管。 酸性溶液精製裝置亦可具備用來將精製處理後的離子交換樹脂再生之再生手段。 [實施例] The refining method of the present invention described above is an acidic solution refining device, which is characterized by having an ion exchange resin refining means and an acidic solution refining means, wherein The ion exchange resin purification means is to obtain a purified cation exchange resin by contacting a mineral acid solution with a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more with the ion exchange resin of the object, and making the concentration 3 The total metal impurity dissolution amount that dissolves when the hydrochloric acid of weight % passes through aforementioned refining ion-exchange resin with volume ratio 25 times amount is below 5 μ g/mL-R, The means for refining the acidic solution is to use the aforementioned refined ion exchange resin to refine the acidic solution; Specifically, an ion-exchange resin column (first column) is provided as an ion-exchange resin to be purified by contacting a mineral acid solution containing a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more. Purification means for obtaining purified ion exchange resin, and the first column is provided with piping for supplying mineral acid for refining ion exchange resin, and piping for discharging waste liquid after purification treatment. In addition, the acidic solution purification device is equipped with an ion exchange resin column (second column) as an acidic solution purification means that further makes the purified ion exchange resin obtained by the ion exchange resin purification means contact the treatment liquid to be purified, and the The second column is provided with a pipe for supplying the acidic solution to be purified and a pipe for discharging the acidic solution after the refining treatment. The acidic solution refining device may also include regeneration means for regenerating the ion exchange resin after the refining treatment. [Example]

以下藉由實施例而具體說明本發明，但本發明並未限定於以下的實施例。The present invention will be specifically described below by way of examples, but the present invention is not limited to the following examples.

＜離子交換樹脂＞ 使用之離子交換樹脂係如以下。 [表1] 試驗 編號 樹脂品名 1 ORLITE DS-1 2 ORLITE DS-4 3 DOWEX TapTec350UPS Na 4 DOWEX Monosphere 99K/350 5 AMBERLITE HPR1006NNC H 6 ORLITE DS-21 7 ORLITE DS-2 8 DOWEX TapTec350UPS Na 試驗編號1及2：強酸性陽離子交換樹脂，粒徑係純水製造所使用之通常的範圍。 試驗編號3：小粒徑且低交聯的強酸性陽離子樹脂。 試驗編號4：小粒徑的強酸性陽離子樹脂。 試驗編號5：高交聯度的強陽離子樹脂，粒徑係純水製造所使用之通常的範圍。 試驗編號6：螯合樹脂，粒徑係純水製造所使用之通常的範圍。 試驗編號7：強鹼性陰離子交換樹脂，粒徑係純水製造所使用之通常的範圍。 試驗編號8：與試驗編號4相同樹脂。但金屬溶出量未滿足5μg/mL-R以下。 <Ion exchange resin> The ion exchange resin used is as follows. [Table 1] Test No. Resin product name 1 ORLITE DS-1 2 ORLITE DS-4 3 DOWEX TapTec350UPS Na 4 DOWEX Monosphere 99K/350 5 AMBERLITE HPR1006NNC H 6 ORLITE DS-21 7 ORLITE DS-2 8 DOWEX TapTec350UPS Na Test No. 1 and 2: strongly acidic cation exchange resin, the particle size is in the usual range used in pure water production. Test No. 3: Strongly acidic cationic resin with small particle size and low crosslinking. Test No. 4: Strongly acidic cationic resin with small particle size. Test No. 5: A strong cationic resin with a high degree of cross-linking, the particle size is in the usual range used in pure water production. Test No. 6: Chelating resin, the particle size is in the usual range used in pure water production. Test No. 7: Strongly basic anion exchange resin, the particle size is in the usual range used in pure water production. Test No. 8: The same resin as Test No. 4. However, the amount of metal elution did not satisfy 5 μg/mL-R or less.

＜離子交換樹脂之精製＞ 試驗編號1~7之離子交換樹脂係使用鹽酸而精製，精製直到在使濃度3重量%的鹽酸以體積比25倍量通過時溶出之總金屬雜質溶出量滿足5μg/mL-R以下。 試驗編號8之樹脂係實施使用鹽酸而變換為H型之處理，但未滿足前述的條件(總金屬雜質溶出量為5μg/mL-R以上)。 ＜Refinement of ion exchange resin＞ The ion exchange resins of test numbers 1 to 7 were purified using hydrochloric acid until the amount of total metal impurities eluted when 3% by weight hydrochloric acid was passed through in an amount 25 times the volume ratio satisfies 5 μg/mL-R or less. The resin of Test No. 8 was treated with hydrochloric acid to convert to H-type, but it did not meet the aforementioned conditions (the eluted amount of total metal impurities was 5 μg/mL-R or more).

1.有機酸中的金屬去除試驗 依照以下的試驗順序，比較各種離子交換樹脂之有機酸中的金屬去除性能。使用檸檬酸(99.9%、和光特級500g、富士軟片和光純藥公司製)作為有機酸。 1. Metal removal test in organic acids According to the following test sequence, the metal removal performance of various ion exchange resins in organic acids was compared. As the organic acid, citric acid (99.9%, 500 g of Wako special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used.

＜試驗順序＞ 於事先洗淨之高密度聚乙烯(HDPE)製批次容器投入各試驗之離子交換樹脂之水溼潤品。將樹脂體積之5倍量的30%檸檬酸移至批次容器，重複2次每5分鐘攪拌容器約10秒鐘並浸漬15分鐘之操作，將離子交換樹脂內的水分與有機酸交換。 此後，將樹脂體積之10倍量的30%檸檬酸移至批次容器，重複4次每15分鐘攪拌容器約10秒鐘之操作。將上澄液適當稀釋，使用ICP-MS而分析金屬濃度。 <Test sequence> Water-wet products of ion exchange resins for each test were put into pre-washed high-density polyethylene (HDPE) batch containers. Move 30% citric acid 5 times the volume of the resin to the batch container, repeat the operation of stirring the container for about 10 seconds every 5 minutes and soaking for 15 minutes twice to exchange the moisture in the ion exchange resin with the organic acid. Thereafter, 30% citric acid, which is 10 times the volume of the resin, was transferred to the batch container, and the operation of stirring the container for about 10 seconds every 15 minutes was repeated 4 times. The supernatant was appropriately diluted, and the metal concentration was analyzed using ICP-MS.

＜結果＞ 將相對於離子交換樹脂處理前的檸檬酸溶液中的金屬濃度之去除率示於表2。作為強酸性陽離子交換樹脂，相較於通常的粒徑(＞400μm以上)，小粒徑樹脂(＜400μm)在Mg、Ca顯示良好的去除率。除此之外，關於Na、Al、Fe亦顯示50%以上的去除率。但是任一強酸性陽離子樹脂皆無法去除As，由於可利用強鹼性陰離子樹脂來減少，因此茲認為其係以陰離子形態存在。 <Result> Table 2 shows the removal rate with respect to the metal concentration in the citric acid solution before the ion exchange resin treatment. As a strongly acidic cation exchange resin, compared with the usual particle size (>400 μm or more), the small particle size resin (<400 μm) shows a good removal rate of Mg and Ca. In addition, Na, Al, and Fe also showed a removal rate of 50% or more. However, any strongly acidic cationic resin cannot remove As, and since it can be reduced by using a strongly basic anionic resin, it is considered that it exists in the form of anion.

2.再生後的金屬去除性 關於經以藉由鹽酸所為之以下的再生方法再生後的各種離子交換樹脂，依照與前述1相同的順序，比較有機酸檸檬酸(99.9%、和光特級500g、富士軟片和光純藥公司製)中的金屬去除性能。此外，本試驗省略在前述1之試驗中金屬去除性能不佳的螯合樹脂與強陰離子樹脂。 2. Metal removability after regeneration With regard to various ion exchange resins regenerated by the following regeneration method with hydrochloric acid, the organic acid citric acid (99.9%, Wako Special Grade 500g, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was compared in the same procedure as 1 above. metal removal performance. In addition, this test omits chelating resins and strong anion resins that have poor metal removal performance in the previous test 1.

＜再生方法＞ 將實施了批次試驗後之離子交換樹脂利用超純水來充分洗淨後，重複6次浸漬於體積之5倍量的1mol/L的鹽酸15分鐘之操作。此後利用超純水來充分洗淨，作成再生樹脂。 ＜Regeneration method＞ The ion exchange resin after the batch test was thoroughly washed with ultrapure water, and then the operation of immersing in 1 mol/L hydrochloric acid of 5 times the volume for 15 minutes was repeated 6 times. Thereafter, it is sufficiently washed with ultrapure water to prepare a recycled resin.

＜結果＞ 將樹脂處理前的檸檬酸溶液中的金屬雜質之去除率示於表3，亦將表2與表3之差作為長條圖示於圖1。若再生前後的去除率之差大，則表示再生不充分且批次試驗第2次的金屬去除性降低。 由表2、3及圖1，可知若比較Na金屬去除率之差，則小粒徑樹脂的試驗編號3、4之離子交換樹脂幾乎未受到再生之影響。 又，就Mg、Ca、Fe之去除率，亦小粒徑樹脂的試驗編號3、4之離子交換樹脂之去除率之差比其它離子交換樹脂更小，顯示良好的結果。若比較小粒徑樹脂彼此，則就Mg、Al、Ca之去除率係低交聯的試驗編號4之離子交換樹脂之去除率之差更小，再生後亦顯示更安定之去除性能。 因此可知小粒徑樹脂係比通常粒徑的樹脂更適合有機酸精製及伴隨再生步驟之有機酸精製，尤其低交聯的小粒徑樹脂顯示更優異的性能。 <Result> The removal rate of metal impurities in the citric acid solution before resin treatment is shown in Table 3, and the difference between Table 2 and Table 3 is also shown in FIG. 1 as a bar graph. If the difference in the removal rate before and after the regeneration is large, the regeneration is insufficient and the metal removal performance in the second run of the batch test is lowered. From Table 2, 3 and Figure 1, it can be seen that if the difference in the removal rate of Na metal is compared, the ion exchange resins of the test numbers 3 and 4 of the small particle size resin are hardly affected by the regeneration. Also, regarding the removal rates of Mg, Ca, and Fe, the difference between the removal rates of the ion-exchange resins of test numbers 3 and 4 of the small-particle-diameter resins was smaller than that of other ion-exchange resins, showing good results. If the resins with smaller particle diameters are compared, the removal rate of Mg, Al, and Ca is lower than that of the ion-exchange resin of Test No. 4, which has lower crosslinking, and the removal rate difference is smaller, and it also shows more stable removal performance after regeneration. Therefore, it can be seen that resins with small particle diameters are more suitable for organic acid purification and organic acid purification accompanied by regeneration steps than resins with normal particle diameters, especially resins with low crosslinking and small particle diameters show better performance.

3.從礦酸去除金屬之試驗 ＜試驗順序＞ 於事先洗淨之HDPE製批次容器投入各試驗之離子交換樹脂之溼潤品。將樹脂體積之10倍量的3.5%鹽酸移至批次容器，重複4次每15分鐘攪拌容器約10秒鐘之操作。將上澄液適當稀釋，使用ICP-MS而分析金屬濃度。 3. Test of metal removal from mineral acid <Test sequence> Wet products of ion exchange resins for each test were put into pre-washed HDPE batch containers. Transfer 3.5% hydrochloric acid 10 times the volume of the resin to the batch container, and repeat the operation of stirring the container for about 10 seconds every 15 minutes 4 times. The supernatant was appropriately diluted, and the metal concentration was analyzed using ICP-MS.

＜結果＞ 將相對於離子交換樹脂處理前的鹽酸溶液中的金屬濃度之去除率示於表4。 在使濃度3重量%的鹽酸以體積比25倍量通過時溶出之總金屬雜質溶出量已減少為5μg/mL-R以下之試驗編號1、4之離子交換樹脂可確認到金屬減少效果。關於鹽酸精製，不太能看到粒徑、交聯度所致之差異，但兩種離子交換樹脂皆得到一定的減少效果。 然而金屬雜質溶出量未滿足5μg/mL-R以下之試驗編號8之離子交換樹脂，可確認到因從樹脂溶出之金屬而導致處理液中的金屬濃度比起處理前更上升。 <Result> Table 4 shows the removal rate with respect to the metal concentration in the hydrochloric acid solution before the ion exchange resin treatment. The metal reduction effect was confirmed for the ion exchange resins of Test Nos. 1 and 4 whose eluted total metal impurities were reduced to 5 μg/mL-R or less when hydrochloric acid with a concentration of 3% by weight was passed in an amount 25 times the volume ratio. Regarding the purification of hydrochloric acid, the difference due to the particle size and degree of cross-linking was hardly seen, but both ion exchange resins obtained a certain reduction effect. However, in the ion exchange resin of Test No. 8 whose elution amount of metal impurities did not satisfy 5 μg/mL-R or less, it was confirmed that the metal concentration in the treatment liquid was higher than that before the treatment due to the metal eluted from the resin.

[表2] 表2.檸檬酸精製試驗結果 試驗編號 1 2 3 4 5 6 7 元素 種類 SAC SAC SAC SAC SAC 螯合 SBA 調和平均徑(μm) ＞400 ＞400 ＜400 ＜400 ＞400 ＞400 ＞400 交聯度(%) ＞12 ＞12 ＞12 ＜12 ＞15 - - Na去除率(%) 68 76 65 63 74 5 ＜5 Mg去除率(%) 106 94 113 109 86 8 ＜5 Al去除率(%) 72 33 103 65 57 ＜5 10 Ca去除率(%) 87 81 100 98 80 ＜5 ＜5 Fe去除率(%) 62 67 72 89 48 ＜5 50 As去除率(%) ＜5 ＜5 ＜5 ＜5 ＜5 ＜5 82 [Table 2] Table 2. Citric acid refining test results Test No. 1 2 3 4 5 6 7 element type SAC SAC SAC SAC SAC Chelation SBA Harmonic mean diameter (μm) >400 >400 <400 <400 >400 >400 >400 Degree of cross-linking (%) >12 >12 >12 <12 >15 - - Na removal rate (%) 68 76 65 63 74 5 <5 Mg removal rate (%) 106 94 113 109 86 8 <5 Al removal rate (%) 72 33 103 65 57 <5 10 Ca removal rate (%) 87 81 100 98 80 <5 <5 Fe removal rate (%) 62 67 72 89 48 <5 50 As removal rate (%) <5 <5 <5 <5 <5 <5 82

[表3] 表3.再生後的檸檬酸精製試驗結果 試驗編號 1 2 3 4 5 元素 種類 SAC SAC SAC SAC SAC 調和平均徑(μm) ＞400 ＞400 ＜400 ＜400 ＞400 交聯度(%) ＞12 ＞12 ＞12 ＜12 ＞15 Na去除率(%) 50 56 70 62 60 Mg去除率(%) 57 56 85 89 53 Al去除率(%) 48 46 75 81 32 Ca去除率(%) 51 54 84 88 57 Fe去除率(%) 48 48 64 78 30 [table 3] Table 3. Results of citric acid refining test after regeneration Test No. 1 2 3 4 5 element type SAC SAC SAC SAC SAC Harmonic mean diameter (μm) >400 >400 <400 <400 >400 Degree of cross-linking (%) >12 >12 >12 <12 >15 Na removal rate (%) 50 56 70 62 60 Mg removal rate (%) 57 56 85 89 53 Al removal rate (%) 48 46 75 81 32 Ca removal rate (%) 51 54 84 88 57 Fe removal rate (%) 48 48 64 78 30

[表4] 表4.鹽酸精製試驗結果 試驗編號 1 4 8 元素 種類 SAC SAC SAC 調和平均徑(μm) ＞400 ＜400 ＜400 交聯度(%) ＞12 ＜12 ＞12 Na去除率(%) ＜10 ＜10 比處理前更增加 Mg去除率(%) 36 23 比處理前更增加 Al去除率(%) 47 46 比處理前更增加 Ca去除率(%) 22 24 比處理前更增加 Fe去除率(%) 37 41 比處理前更增加 [Table 4] Table 4. Hydrochloric acid refining test results Test No. 1 4 8 element type SAC SAC SAC Harmonic mean diameter (μm) >400 <400 <400 Degree of cross-linking (%) >12 <12 >12 Na removal rate (%) <10 <10 more than before treatment Mg removal rate (%) 36 twenty three more than before treatment Al removal rate (%) 47 46 more than before treatment Ca removal rate (%) twenty two twenty four more than before treatment Fe removal rate (%) 37 41 more than before treatment

茲詳細揭示並說明本發明之數個較佳的實施形態，但請理解本發明可未脫離添附之發明申請專利範圍之主旨或範圍而進行各種變更及修正。Several preferred embodiments of the present invention are hereby disclosed and described in detail, but please understand that the present invention can undergo various changes and amendments without departing from the gist or scope of the appended invention patent scope.

無none

【圖1】圖1係表示再生前與再生後的檸檬酸精製試驗之檸檬酸溶液中的金屬雜質之去除率之差之圖表。[Fig. 1] Fig. 1 is a graph showing the difference in removal rate of metal impurities in citric acid solution in citric acid purification test before regeneration and after regeneration.

Claims (8)

一種酸性溶液之精製方法，係使用離子交換樹脂之酸性溶液之精製方法，其特徵為： 該離子交換樹脂係藉由使金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸精製對象的離子交換樹脂而進行精製從而得到的精製離子交換樹脂，且在使濃度3重量%的鹽酸以體積比25倍量通過該精製離子交換樹脂時溶出之總金屬雜質溶出量為5μg/mL-R以下。 A method for refining an acidic solution is a method for refining an acidic solution using an ion exchange resin, and is characterized in that: This ion exchange resin is a purified ion exchange resin obtained by making a mineral acid solution with a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more contact with the ion exchange resin to be purified, and the concentration is 3 When weight % hydrochloric acid passes through the purified ion exchange resin in an amount 25 times the volume ratio, the total metal impurities dissolved out are below 5 μg/mL-R. 如請求項1之酸性溶液之精製方法，其中該礦酸溶液中的鈉(Na)、鈣(Ca)、鎂(Mg)、及鐵(Fe)之含量分別為200μg/L以下。A method for refining an acidic solution as claimed in claim 1, wherein the contents of sodium (Na), calcium (Ca), magnesium (Mg), and iron (Fe) in the mineral acid solution are respectively below 200 μg/L. 如請求項1或2之酸性溶液之精製方法，其中該離子交換樹脂包含苯乙烯型強酸性離子交換樹脂。The purification method of the acidic solution as claimed in item 1 or 2, wherein the ion exchange resin comprises a styrene-type strongly acidic ion exchange resin. 如請求項3之酸性溶液之精製方法，其中該苯乙烯型強酸性離子交換樹脂之調和平均徑為100μm以上且400μm以下。The method for purifying an acidic solution according to claim 3, wherein the harmonic mean diameter of the styrene-type strongly acidic ion exchange resin is not less than 100 μm and not more than 400 μm. 一種酸性溶液精製用離子交換樹脂之再生方法，其特徵為使使用如請求項1或2之精製方法而將酸溶液精製後的離子交換樹脂接觸礦酸溶液後，實施水洗淨直到洗淨水之TOC達30ppb以下。A method for regenerating an ion-exchange resin for refining an acidic solution, characterized in that the ion-exchange resin after refining the acid solution is contacted with the mineral acid solution by using the refining method of claim 1 or 2, and then washed with water until the water is cleared. The TOC is below 30ppb. 如請求項1或2之酸性溶液之精製方法，其中使用藉由如請求項5之再生方法而再生之再生離子交換樹脂作為該離子交換樹脂。The method for purifying an acidic solution according to claim 1 or 2, wherein a regenerated ion exchange resin regenerated by the regeneration method according to claim 5 is used as the ion exchange resin. 一種酸性溶液精製裝置，其特徵為具備離子交換樹脂精製手段、與酸性溶液精製手段，其中 該離子交換樹脂精製手段係藉由使金屬雜質量為1mg/L以下且濃度為5重量%以上的礦酸溶液接觸對象的離子交換樹脂而進行精製從而得到精製陽離子交換樹脂，且在使濃度3重量%的鹽酸以體積比25倍量通過該精製離子交換樹脂時溶出之總金屬雜質溶出量為5μg/mL-R以下， 該酸性溶液精製手段係使用該精製離子交換樹脂而將酸性溶液精製。 An acidic solution refining device is characterized in that it has ion exchange resin refining means and acidic solution refining means, wherein The ion exchange resin purification means is to obtain a purified cation exchange resin by contacting a mineral acid solution with a metal impurity amount of 1 mg/L or less and a concentration of 5% by weight or more with the ion exchange resin of the object, and making the concentration 3 When the hydrochloric acid of % by weight passes through this refined ion exchange resin with a volume ratio of 25 times, the total metal impurity dissolution amount dissolved is below 5 μg/mL-R, The means for refining the acidic solution is to refine the acidic solution using the purified ion exchange resin. 如請求項7之酸溶液精製裝置，其具有酸性溶液之精製後的離子交換樹脂之再生手段。The acid solution refining device as claimed in claim 7, which has means for regenerating the ion exchange resin after the acid solution is purified.
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