WO2001074488A1 - Method for preparing acidic cation exchange resin fixed bed for producing bisphenols - Google Patents
Method for preparing acidic cation exchange resin fixed bed for producing bisphenols Download PDFInfo
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- WO2001074488A1 WO2001074488A1 PCT/JP2001/002588 JP0102588W WO0174488A1 WO 2001074488 A1 WO2001074488 A1 WO 2001074488A1 JP 0102588 W JP0102588 W JP 0102588W WO 0174488 A1 WO0174488 A1 WO 0174488A1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- 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
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- 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
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
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- 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
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/347—1,2-additions, e.g. aldol or Knoevenagel condensations via cationic intermediates, e.g. bisphenol A type processes
Definitions
- the present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols, and more particularly, to a bisphenol in which an acidic cation exchange resin is uniformly partially neutralized with a nitrogen-containing sulfur compound.
- the present invention relates to a method for preparing a fixed bed of an acid- and ion-exchange resin for the production of oils.
- Bisphenols for example, 2,2-bis (4-hydroxyphenol) propane (hereinafter abbreviated as bisphenol A), are engineered plastics such as polycarbonate resin, resin and polyarylate resin. It is known that it is an important compound as a raw material such as epoxy resin or epoxy resin, and its demand has been increasing in recent years. Bisphenols including bisphenol A are produced by reacting phenols with carbonyl compounds using a fixed bed of an acidic cation exchange resin (hereinafter, also simply referred to as ion exchange resin) as a catalyst. Is known.
- an acidic cation exchange resin hereinafter, also simply referred to as ion exchange resin
- Japanese Patent Publication No. Sho 62-748 discloses an ion exchange resin fixed bed. A method of circulating a liquid in which hydrochloric acid is added is disclosed. However, there is a problem of equipment corrosion due to the use of hydrochloric acid. Also, Japanese Patent Application Laid-Open No. 8-49061 discloses a method in which aromatic sulfonates are added to a nitrogen-containing sulfur compound as a neutralizing agent, but aromatic sulfonic acids have a problem of corrosion. However, if the ion-exchange resin is replaced with water-washed phenol, there is a problem in that the acid is poorly cut, which adversely affects the quality of the product at the start of the reaction. Therefore, a neutralization method that does not require the addition of an acid has been desired. Disclosure of the invention
- the present invention has been made in view of the above, and it is an object of the present invention to provide a method for preparing a fixed bed of an ion exchange resin for producing bisphenols, which does not require the addition of an acid.
- the present inventors have conducted intensive studies and found that the reactor was filled with an acidic ion-exchange resin to form a fixed bed, and then washed with water before the start of the reaction.
- the inventors have found that the object of the present invention can be effectively achieved by charging an aqueous solution in which a sulfur compound is dissolved into the reactor and circulating the aqueous solution, thereby completing the present invention.
- the gist of the present invention is as follows.
- the reactor is filled with acidic cation exchange resin. After forming a fixed bed and before starting the reaction, the reactor is washed with water, and an aqueous solution in which a nitrogen-containing sulfur compound is dissolved in the discharged washing water is charged into the reactor and circulated.
- a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols 2. The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to the above item 1, wherein the acidic cation exchange resin is a sulfonic acid type ion exchange resin.
- bisphenols are produced by reacting phenols with carbonyl compounds.
- phenols have no substituent at the para-position to the hydroxyl group.
- alkylphenols such as phenol, 0-cresol, m-cresol, 0-tert-butylphenol, 2,6-xylenol, 2,6-di-tert-butylphenol, and 0-chloro
- examples thereof include halogenated phenols such as phenol, m-chlorophenol, and 2,6-dichlorophenol.
- the carbonyl compound include 'acetone, methylethylenoketone, and methylisobutyl phenol. Tontone, methyl-n-propylketon: ketones such as acetophphenone and cyclohexanone, and aldehydes such as formalin, acetaldehyde and benzaldehyde.
- the present invention provides a method for producing bis (acetylene) and phenol Applicable for the production of phenol A.
- the acidic cation exchange resin used as the catalyst is preferably a sulfonic acid-based resin, and the base resin is styrene-divinylbenzene copolymer, perfluoroethylene copolymer, or phenol-formaldehyde. Styrene-divinylbenzene copolymer system is preferred. These resins can be used in either a gel type or a porous type, but the degree of crosslinking is preferably relatively low, for example, 2 to 8%. This acidic cation exchange resin is filled in a reactor to form a fixed bed.
- the reactor is filled with an acidic cation-exchange resin to form a fixed bed, and then washed with water before the start of the reaction, and the nitrogen-containing sulfur compound is dissolved in the effluent washing water.
- An aqueous solution is charged to the reactor and circulated, so that the acidic cation exchange resin is partially neutralized uniformly with the nitrogen-containing sulfur compound.
- the amount of water used for washing with water is preferably 0.5 to 2 times the volume of the ion-exchange resin in a water-swelled state.
- an aqueous solution in which the nitrogen-containing sulfur compound is dissolved in the wash water that has flowed out is charged into the reactor and circulated.
- nitrogen-containing sulfur compounds examples include mercaptoalkylamines such as 2-mercaptoethylamine, 3-mercaptobutylamine, 2,2-dimethylthiazolidin, and 2-methyl-2-ethylthiazolidin.
- Thiazolidines such as cycloalkylthiazolidine, 2-methyl-2-phenylthiazolidine, 3-methylthiazolidin, and aminothiophenols such as 1,4-aminothiophenol;
- the concentration of the aqueous solution of the nitrogen-containing sulfur compound may be dissolved in washing water, preferably 1 to 10% by mass, and the total amount is preferably based on the sulfonic acid groups in the acidic cation exchange resin. It is preferably 2 to 50 mol%, more preferably 5 to 30 mol%.
- the circulation of the nitrogen-containing sulfur compound aqueous solution may be performed until a desired neutralization ratio of the ion exchange resin is reached.
- the desired neutralization ratio is 2 to 5.0%, preferably 5 to 30%. If the neutralization ratio is too low or too high, sufficient catalytic activity cannot be exhibited. .
- the neutralization may be performed at room temperature or at a temperature of 30 to 100 ° C. If the temperature exceeds 100 ° C., elimination of sulfonic acid from the ion-exchange resin becomes severe, which is not preferable.
- the neutralization rate of the ion exchange resin was determined in the same manner as in Example 1, except that pure water was used instead of the washed out water. Table 1 shows the results. Table 1 Neutralization rate (%)
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Abstract
Description
明 細 書 ビスフ ノ一ル類製造用酸性陽ィォン交換樹脂固定床の調製方法 技術分野 Description Method for preparing fixed bed of acidic cation-exchange resin for the production of bisphenols
本発明は、 ビスフエノ一ル類製造用酸性陽イオン交換樹脂固定床 の調製方法に関し、 さ らに詳しく は、 酸性陽イオン交換樹脂が含窒 素硫黄化合物で均一に部分中和されたビスフ ノ一ル類製造用酸性 陽ィォン交換樹脂固定床の調製方法に関する。 背景技術 The present invention relates to a method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols, and more particularly, to a bisphenol in which an acidic cation exchange resin is uniformly partially neutralized with a nitrogen-containing sulfur compound. The present invention relates to a method for preparing a fixed bed of an acid- and ion-exchange resin for the production of oils. Background art
ビスフエノール類、 例えば 2， 2 — ビス （ 4 — ヒ ドロキシフエ二 ル） プロパン （以下、 ビスフヱノール Aと略称する。 ） は、 ポリ 力 一ボネ一 卜.樹脂ゃポリアリ レー 卜樹脂などのエンジニアリ ンダプラ スチック、 あるいはエポキシ樹脂などの原料として重要な化合物で あることが知られており、 近年その需要はますます増大する傾向に ある。 このビスフエノール Aをはじめとするビスフエノール類は、 触媒として酸性陽イオン交換樹脂 （以下、 単にイオン交換樹脂とも いう。 ） 固定床を使用し、 フエノール類とカルボニル化合物とを反 応させて製造されることは公知である。 また、 その場合、 ビスフエ ノ一ル Aを例に採れば、 異性体である 2— ( 2 —ヒ ドロキシフェニ ル） 一 2 — （ 4 ーヒ ドロキシフェニル） プロパンの副生を抑えるた めに、 ィォン交換樹脂を含窒素硫黄化合物で均一に部分中和したも のを触媒と して使用すること.も知られており、 その中和法と してい ろいろな方法が試みられている。 Bisphenols, for example, 2,2-bis (4-hydroxyphenol) propane (hereinafter abbreviated as bisphenol A), are engineered plastics such as polycarbonate resin, resin and polyarylate resin. It is known that it is an important compound as a raw material such as epoxy resin or epoxy resin, and its demand has been increasing in recent years. Bisphenols including bisphenol A are produced by reacting phenols with carbonyl compounds using a fixed bed of an acidic cation exchange resin (hereinafter, also simply referred to as ion exchange resin) as a catalyst. Is known. In that case, taking bisphenol A as an example, to suppress the by-product of the isomer 2- (2-hydroxyphenyl) -12- (4-hydroxyphenyl) propane, It is also known to use, as a catalyst, a partially neutralized ion-exchange resin uniformly with a nitrogen-containing sulfur compound, and various neutralization methods have been tried.
例えば、 特公昭 6 2 - 7 4 8号公報には、 ィォン交換樹脂固定床 中に塩酸を添加した液体を循環させる方法が開示されている。 しか し、 塩酸の使用により装置の腐食の問題がある。 また、 特開平 8 - 4 0 9 6 1号公報には、 中和剤の含窒素硫黄化合物に芳香族スルホ ン酸類を添加する方法が開示されているが、 芳香族スルホン酸類は 腐食の問題はないが、 ィォン交換樹脂を水洗浄ゃフ二ノールで置換 する場合、 酸の切れが悪く なり、 その結果反応開始時の製品の品質 に悪影響を及ぼすという問題がある。 したがって、 酸の添加の必要 のない中和方法が望まれていた。 発明の開示 For example, Japanese Patent Publication No. Sho 62-748 discloses an ion exchange resin fixed bed. A method of circulating a liquid in which hydrochloric acid is added is disclosed. However, there is a problem of equipment corrosion due to the use of hydrochloric acid. Also, Japanese Patent Application Laid-Open No. 8-49061 discloses a method in which aromatic sulfonates are added to a nitrogen-containing sulfur compound as a neutralizing agent, but aromatic sulfonic acids have a problem of corrosion. However, if the ion-exchange resin is replaced with water-washed phenol, there is a problem in that the acid is poorly cut, which adversely affects the quality of the product at the start of the reaction. Therefore, a neutralization method that does not require the addition of an acid has been desired. Disclosure of the invention
本発明は、 上記観点からなされたもので、 酸の添加を必要と しな ぃビスフエノール類製造用陽ィォン交換樹脂固定床の調製方法を提 供することを目的と'するものである。 The present invention has been made in view of the above, and it is an object of the present invention to provide a method for preparing a fixed bed of an ion exchange resin for producing bisphenols, which does not require the addition of an acid.
本発明者らは鋭意研究を重ねた結果、 反応器に酸性陽ィォン交換 樹脂を充塡し固定床を形成させた後、 反応開始前に、 水で洗浄し、 その流出した洗浄水に含窒素硫黄化合物を溶解させた水溶液を該反 応器に装入し、 循環させることにより、 上記発明の目的を効桌的に 達成しうることを見出し本発明を完成させたものである。 The present inventors have conducted intensive studies and found that the reactor was filled with an acidic ion-exchange resin to form a fixed bed, and then washed with water before the start of the reaction. The inventors have found that the object of the present invention can be effectively achieved by charging an aqueous solution in which a sulfur compound is dissolved into the reactor and circulating the aqueous solution, thereby completing the present invention.
すなわち、 本 ¾明の要旨は下記のとおりである。 That is, the gist of the present invention is as follows.
1 . 酸性陽イオン交換樹脂が含窒素硫黄化合物で均一に部分中和さ れたビスフユノ一ル類製造用酸性陽ィォン交換樹脂固定床の調製方 法において、 反応器に酸性陽イオン交換樹脂を充填し固定床を形成 させた後、 反応開始前に、 水で洗浄し、 その流出した洗浄水に含窒 素硫黄化合物を溶解させた水溶液を該反応器に装入し、 循環させる こ とを特徵とするビスフ ノ一ル類製造用酸性陽イオン交換樹脂固 定床の調製方法。 2 . 酸性陽ィォン交換樹脂がスルホン酸型陽ィォン交換樹脂である 前記 1記載のビスフ ノ—ル類製造用酸性陽ィォン交換樹脂固定床 の調製方法。 1. In the method for preparing a fixed bed of acidic cation exchange resin for the production of bisphenols, in which the acidic cation exchange resin is uniformly partially neutralized with nitrogen-containing sulfur compounds, the reactor is filled with acidic cation exchange resin. After forming a fixed bed and before starting the reaction, the reactor is washed with water, and an aqueous solution in which a nitrogen-containing sulfur compound is dissolved in the discharged washing water is charged into the reactor and circulated. A method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols. 2. The method for preparing a fixed bed of an acidic cation exchange resin for producing bisphenols according to the above item 1, wherein the acidic cation exchange resin is a sulfonic acid type ion exchange resin.
4 . 含窒素硫黄化合物がメルカプトアルキルァミ ン類又はチアゾリ ジン類である前記 1又は 2に記載のビスフユノ一ル類製造用酸性陽 ィオン交換樹脂固定床の調製方法。 4. The method for preparing a fixed bed of an acidic cation-exchange resin for the production of bisphenols according to the above 1 or 2, wherein the nitrogen-containing sulfur compound is a mercaptoalkylamine or a thiazolidin.
5 . ビスフエノール類が 2 , 2 — ビス （ 4 ー ヒ ドロキシフエニル） プロパンである前記 1〜 3のいずれかに記載のビスフヱノ一ル類製 造用酸性陽ィォン交換樹脂固定床の調製方法。 発明を実施するための最良の形態 5. The method for preparing an acidic ion-exchange resin fixed bed for producing bisphenols according to any one of the above items 1 to 3, wherein the bisphenol is 2,2-bis (4-hydroxyphenyl) propane. BEST MODE FOR CARRYING OUT THE INVENTION
以下に、 本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において、 ビスフエノール類は、 フエノール類とカルボ二 ル化合物とを反応させて製造される。 ' In the present invention, bisphenols are produced by reacting phenols with carbonyl compounds. '
フエノール類は、 水酸基に対してパラ位に置換基を有しないこと が必要である。 具体的には、 フエノール、 0 —ク レゾール、 m —ク レゾール、 0 — t e r t —プチルフエノール、 2 , 6 —キシレノ一 ル、 2， 6 —ジー t e r t —プチルフエノール等のアルキルフエノ 一ノレや 0 —ク ロ口フエノール、 m —クロ口フエノール、 2， 6 —ジ クロロフヱノール等のハロゲン化フヱノールを挙げることができる, カルボニル化合物としては、 具体的には、 'アセ トン， メチルエチ ノレケ ト ン， メチルイソプチルケ ト ン， メチルー n—プロピルケ ト ン: ァセ トフエノ ン， シクロへキサノ ン等のケ ト ン類やホルマリ ン， ァ セ トアルデヒ ド， ベンズアルデヒ ド等のアルデヒ ド類を挙げること ができる。 It is necessary that phenols have no substituent at the para-position to the hydroxyl group. Specifically, alkylphenols such as phenol, 0-cresol, m-cresol, 0-tert-butylphenol, 2,6-xylenol, 2,6-di-tert-butylphenol, and 0-chloro Examples thereof include halogenated phenols such as phenol, m-chlorophenol, and 2,6-dichlorophenol. Specific examples of the carbonyl compound include 'acetone, methylethylenoketone, and methylisobutyl phenol. Tontone, methyl-n-propylketon: ketones such as acetophphenone and cyclohexanone, and aldehydes such as formalin, acetaldehyde and benzaldehyde.
好適には、 本発明は、 アセ ト ンとフエノールを原料とするビス フヱノール Aの製造に適用できる。 Preferably, the present invention provides a method for producing bis (acetylene) and phenol Applicable for the production of phenol A.
触媒と して使用する酸性陽イオン交換樹脂は、 スルホン酸系のも のが好ま しく、 母体となる樹脂としては、 スチレン一ジビニルペン ゼン共重合体系， パーフルォロエチレン共重合体系， フヱノール— ホルムアルデヒ ド重合体系等があるが、 スチレンージビニルベンゼ ン共重合体系が好ま しい。 これらの樹脂はゲル型、 ポーラス型どち らでも使用できるが、 架橋度は、 例えば、 2〜 8 %と比較的低いも のが好ま しい。 この酸性陽イオン交換樹脂を、 反応器に充塡し固定 床を形成させる。 The acidic cation exchange resin used as the catalyst is preferably a sulfonic acid-based resin, and the base resin is styrene-divinylbenzene copolymer, perfluoroethylene copolymer, or phenol-formaldehyde. Styrene-divinylbenzene copolymer system is preferred. These resins can be used in either a gel type or a porous type, but the degree of crosslinking is preferably relatively low, for example, 2 to 8%. This acidic cation exchange resin is filled in a reactor to form a fixed bed.
本発明においては、 反応器に酸性陽イオン.交換樹脂を充塡し固定 床を形成させた後、 反応開始前に、 水で洗浄し、 その流出した洗浄 水に含窒素硫黄化合物を溶解させた水溶液を該反応器に装入し、 循 環させて、 酸性陽イオン交換樹脂を該含窒素硫黄化合物で均一に部 分中和する。 In the present invention, the reactor is filled with an acidic cation-exchange resin to form a fixed bed, and then washed with water before the start of the reaction, and the nitrogen-containing sulfur compound is dissolved in the effluent washing water. An aqueous solution is charged to the reactor and circulated, so that the acidic cation exchange resin is partially neutralized uniformly with the nitrogen-containing sulfur compound.
水での洗浄に使用される水の量は、 水膨潤状態のィォン交換樹脂 の容量の 0 . 5〜 2倍が好適である。 The amount of water used for washing with water is preferably 0.5 to 2 times the volume of the ion-exchange resin in a water-swelled state.
次いで、 流出した洗浄水に含窒素硫黄化合物.を溶解させた水溶液 を反応器に装入し、 循環させるわけである。 Next, an aqueous solution in which the nitrogen-containing sulfur compound is dissolved in the wash water that has flowed out is charged into the reactor and circulated.
上記の含窒素硫黄化合物としては、 例えば、 2 —メルカプトェチ ルァミ ン、 3 —メルカプトプチルァミ ン等のメルカプトアルキルァ ミ ン類、 2， 2 —ジメチルチアゾリ ジン、 2 —メチルー 2 —ェチル チァゾリ ジン、 シクロアルキルチアゾリ ジン、 2 —メチル— 2 — フエ二ルチアゾリ ジン、 3 —メチルチアゾリ ジン等のチアゾリ ジン 類、 1， 4 一アミ ノチオフエノ一ル等のアミ ノチオフエノ一ル類、 Examples of the above nitrogen-containing sulfur compounds include mercaptoalkylamines such as 2-mercaptoethylamine, 3-mercaptobutylamine, 2,2-dimethylthiazolidin, and 2-methyl-2-ethylthiazolidin. Thiazolidines such as cycloalkylthiazolidine, 2-methyl-2-phenylthiazolidine, 3-methylthiazolidin, and aminothiophenols such as 1,4-aminothiophenol;
3 一メルカプトメチルピリ ジン、 3 —メルカプトェチルピリ ジン、3 1-mercaptomethylpyridine, 3—mercaptoethylpyridine,
4 —メルカプトェチルピリ ジン等のメルカプトアルキルピリ ジン類 などを挙げることができるが、 中でもメルカプトアルキルアミ ン類 チアゾリ ジン類が好ましい。 該含窒素硫黄化合物の水溶液の濃度は. 洗浄水に溶解させて、 好ましく は 1〜 1 0質量％にすればよく、 全 使用量は、 酸性陽イオン交換樹脂中のスルホン酸基に対して好まし く は 2〜 5 0モル 、 より好ましく は 5 ~ 3 0 モル％である。 4—Mercaptoalkyl pyridines such as mercaptoethyl pyridine Among them, mercaptoalkylamines and thiazolidines are preferable. The concentration of the aqueous solution of the nitrogen-containing sulfur compound may be dissolved in washing water, preferably 1 to 10% by mass, and the total amount is preferably based on the sulfonic acid groups in the acidic cation exchange resin. It is preferably 2 to 50 mol%, more preferably 5 to 30 mol%.
なお、 含窒素硫黄化合物水溶液の循環は、 イオン交換樹脂の所望 の中和率となるまで行えばよい。 The circulation of the nitrogen-containing sulfur compound aqueous solution may be performed until a desired neutralization ratio of the ion exchange resin is reached.
その所望の中和率は、 2〜 5. 0 %、 好ましく は 5〜 3 0 %である, この中和率が低すぎても、 高すぎても充分な触媒活性を発揮するこ とができない。 The desired neutralization ratio is 2 to 5.0%, preferably 5 to 30%. If the neutralization ratio is too low or too high, sufficient catalytic activity cannot be exhibited. .
中和を行う温度については、 室温でもよいし、 あるいは 3 0 〜 1 0 0 °Cに加温してもよい。 1 0 0 °Cを超えると、 イオン交換樹脂 のスルホン酸の脱離が激しく なり好ましくない。 The neutralization may be performed at room temperature or at a temperature of 30 to 100 ° C. If the temperature exceeds 100 ° C., elimination of sulfonic acid from the ion-exchange resin becomes severe, which is not preferable.
本発明においては、 洗浄水に含まれている酸が効果的に働いたと 推定される。 In the present invention, it is presumed that the acid contained in the washing water worked effectively.
次に、 本発明を実施例により具体的に説明するが、 これらの実施 例になんら制限されるものではない。 Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
〔実施例 1 〕 (Example 1)
内径 2 5 rft m、 長さ 2 0 c mのガラスカラムに水膨潤状態のスル ホン酸型陽イオン交換樹脂 （三菱化学社製、 ダイヤイオン S K - 1 0 4 ) 5 0 c cを充塡し、 これに純水 1 0 0 c cを流通させた。 この流出した水にジメチルチアゾリ ンを 1 . 4 g溶解させ、 イオン 交換樹脂床に 3 0 0 c c / h rで装入、 流出した液は循環させた。 1 2 0時間循環させ、 イオン交換樹脂を 5分割で抜き出して中和率 を調べた。 その結果を第 1表に示す。 なお、 中和率は下記の式で求 めた。 中和率 (%) = 1 0 0 X 1一A glass column with an inner diameter of 25 rft m and a length of 20 cm is filled with 50 cc of a water-swelled sulfonate-type cation exchange resin (Diaion SK-104, manufactured by Mitsubishi Chemical Corporation). 100 cc of pure water was circulated. 1.4 g of dimethylthiazoline was dissolved in the effluent water, charged into the ion-exchange resin bed at 300 cc / hr, and the effluent was circulated. The mixture was circulated for 120 hours, and the ion exchange resin was extracted in five portions and the neutralization ratio was examined. Table 1 shows the results. The neutralization ratio was determined by the following equation. Neutralization rate (%) = 1 0 0 X 1
(上式で、 酸当量は水酸化ナ 卜 リ ゥム水溶液を用いて滴定法で測定 した。 ） (In the above formula, the acid equivalent was measured by a titration method using an aqueous solution of sodium hydroxide.)
〔比較例 1〕 (Comparative Example 1)
実施例 1 において、 流出した洗浄水の代わりに純水を使用したこ と以外は同様に実施しィォン交換樹脂の中和率を求めた。 その結果 を第 1表に示す。 第 1表 中和率（％) The neutralization rate of the ion exchange resin was determined in the same manner as in Example 1, except that pure water was used instead of the washed out water. Table 1 shows the results. Table 1 Neutralization rate (%)
本発明によれば、 酸の添加を必要としないビスフニノール類製造 甩陽ィォン交換樹脂固定床の調製方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the preparation method of a bis-funinol production | generation which does not require addition of an acid can be provided.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000102049A JP2001286770A (en) | 2000-04-04 | 2000-04-04 | Preparation method of fixed bed of acidic cation exchange resin for bisphenol production |
| JP2000-102049 | 2000-04-04 |
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| Publication Number | Publication Date |
|---|---|
| WO2001074488A1 true WO2001074488A1 (en) | 2001-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2001/002588 Ceased WO2001074488A1 (en) | 2000-04-04 | 2001-03-28 | Method for preparing acidic cation exchange resin fixed bed for producing bisphenols |
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| Country | Link |
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| JP (1) | JP2001286770A (en) |
| TW (1) | TW572788B (en) |
| WO (1) | WO2001074488A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6891073B2 (en) | 2002-02-28 | 2005-05-10 | General Electric Company | Chemical reactor system and process |
| US7112702B2 (en) | 2002-12-12 | 2006-09-26 | General Electric Company | Process for the synthesis of bisphenol |
| US7132575B2 (en) | 2003-07-01 | 2006-11-07 | General Electric Company | Process for the synthesis of bisphenol |
| US8932976B2 (en) | 2007-06-14 | 2015-01-13 | Dow Global Technologies Llc | Preparation of catalyst for bisphenols production |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4298438B2 (en) * | 2003-09-01 | 2009-07-22 | 出光興産株式会社 | Method for preparing modified catalyst for production of bisphenol A |
| JP2005074353A (en) * | 2003-09-02 | 2005-03-24 | Idemitsu Kosan Co Ltd | Method for preparing modified catalyst for production of bisphenol A |
| JP4452058B2 (en) * | 2003-11-04 | 2010-04-21 | 出光興産株式会社 | Method for preparing modified catalyst for production of bisphenol A |
| JP4452119B2 (en) * | 2004-04-26 | 2010-04-21 | 出光興産株式会社 | Method for producing catalyst for producing bisphenols |
| JP4971663B2 (en) * | 2006-03-31 | 2012-07-11 | 三井化学株式会社 | Method for preparing catalyst for production of bisphenols |
| CN102471098B (en) * | 2009-06-30 | 2014-01-29 | 栗田工业株式会社 | Ion exchange device and its production method and equipment, and ion exchange resin layer formation method and its device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1539463A (en) * | 1976-07-26 | 1979-01-31 | Shell Int Research | Preparation of a fixed bed catalyst |
| JPH06296871A (en) * | 1993-04-20 | 1994-10-25 | Chiyoda Corp | Method for filling reactor with catalyst for manufacturing bisphenol a |
| JPH06304479A (en) * | 1993-04-20 | 1994-11-01 | Chiyoda Corp | Method for filling catalyst for preparation of bisphenol a in reactor |
| JPH0840961A (en) * | 1994-08-02 | 1996-02-13 | Nippon Steel Chem Co Ltd | Method for preparing fixed bed of acidic cation exchange resin |
-
2000
- 2000-04-04 JP JP2000102049A patent/JP2001286770A/en active Pending
-
2001
- 2001-03-28 WO PCT/JP2001/002588 patent/WO2001074488A1/en not_active Ceased
- 2001-03-30 TW TW90107896A patent/TW572788B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1539463A (en) * | 1976-07-26 | 1979-01-31 | Shell Int Research | Preparation of a fixed bed catalyst |
| JPH06296871A (en) * | 1993-04-20 | 1994-10-25 | Chiyoda Corp | Method for filling reactor with catalyst for manufacturing bisphenol a |
| JPH06304479A (en) * | 1993-04-20 | 1994-11-01 | Chiyoda Corp | Method for filling catalyst for preparation of bisphenol a in reactor |
| JPH0840961A (en) * | 1994-08-02 | 1996-02-13 | Nippon Steel Chem Co Ltd | Method for preparing fixed bed of acidic cation exchange resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6891073B2 (en) | 2002-02-28 | 2005-05-10 | General Electric Company | Chemical reactor system and process |
| US7112702B2 (en) | 2002-12-12 | 2006-09-26 | General Electric Company | Process for the synthesis of bisphenol |
| US7132575B2 (en) | 2003-07-01 | 2006-11-07 | General Electric Company | Process for the synthesis of bisphenol |
| US8932976B2 (en) | 2007-06-14 | 2015-01-13 | Dow Global Technologies Llc | Preparation of catalyst for bisphenols production |
Also Published As
| Publication number | Publication date |
|---|---|
| TW572788B (en) | 2004-01-21 |
| JP2001286770A (en) | 2001-10-16 |
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