JP2002001134A - Method for preserving aminothiol-modified cation exchange resin - Google Patents
Method for preserving aminothiol-modified cation exchange resinInfo
- Publication number
- JP2002001134A JP2002001134A JP2000193699A JP2000193699A JP2002001134A JP 2002001134 A JP2002001134 A JP 2002001134A JP 2000193699 A JP2000193699 A JP 2000193699A JP 2000193699 A JP2000193699 A JP 2000193699A JP 2002001134 A JP2002001134 A JP 2002001134A
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- exchange resin
- aminothiol
- modified
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はスルホン酸型陽イオ
ン交換樹脂のスルホン酸基の一部を、アミノチオール化
合物で変性した、アミノチオール変性陽イオン交換樹脂
の保存方法に関するものである。The present invention relates to a method for preserving an aminothiol-modified cation exchange resin in which a part of sulfonic acid groups of a sulfonic acid type cation exchange resin is modified with an aminothiol compound.
【０００２】[0002]
【従来の技術】スルホン酸基の一部をアミノチオール化
合物で変性したスルホン酸型陽イオン交換樹脂が、フェ
ノール化合物とケトンを反応させてビスフェノールを製
造する反応の触媒として好適なことはよく知られてい
る。スルホン酸型陽イオン交換樹脂は通常はナトリウム
型で市販されているので、このアミノチオール変性陽イ
オン交換樹脂を製造するには、先ずナトリウム型のスル
ホン酸型陽イオン交換樹脂を塩酸などで処理して遊離型
に転換する。次いでこの遊離型の樹脂をアミノチオール
化合物の溶液で処理して、スルホン酸基の一部をアミノ
チオール化合物で変性する。この一連の操作は回分方式
で行われる。そして得られたアミノチオール変性陽イオ
ン交換樹脂は、液切りして保存するか又は水中に保存す
る。2. Description of the Related Art It is well known that a sulfonic acid type cation exchange resin in which a part of sulfonic acid groups is modified with an aminothiol compound is suitable as a catalyst for a reaction for producing bisphenol by reacting a phenol compound with a ketone. ing. Since the sulfonic acid type cation exchange resin is usually commercially available in the form of sodium, to prepare this aminothiol-modified cation exchange resin, the sodium type sulfonic acid type cation exchange resin is first treated with hydrochloric acid or the like. To the free form. Next, this free resin is treated with a solution of an aminothiol compound to partially modify the sulfonic acid group with the aminothiol compound. This series of operations is performed in a batch mode. Then, the obtained aminothiol-modified cation exchange resin is drained and stored, or stored in water.
【発明が解決しようとする課題】アミノチオール変性陽
イオン交換樹脂を触媒として用いるビスフェノールの製
造は、通常はこの樹脂を充填した固定床反応器に、フェ
ノール化合物とケトンを含む原料流体を連続的に流通さ
せることにより行われる。アミノチオール変性陽イオン
交換樹脂の触媒活性は漸次低下するので、数ケ月ないし
は２０ケ月に一度程度の頻度で触媒の入れ替えが行われ
る。前述のように触媒として用いるアミノチオール変性
陽イオン交換樹脂の調製は回分方式で行われるので、触
媒は入れ替えに備えて少量づつ調製して保存しておくの
が普通である。しかし本発明者らの検討によれば、水中
に保存しておくと樹脂の変性率が低下すること、そして
その原因の一半は保存中にアミノチオール化合物が樹脂
から脱離することによることが判明した。所定の変性率
に調整してある触媒からアミノチオール化合物が脱離し
て変性率が低下すると、触媒は所期の性能を示さなくな
る。従って本発明はアミノチオール変性陽イオン交換樹
脂を水中に保存するに際し、アミノチオール化合物の脱
離を抑制する方法を提供しようとするものである。In the production of bisphenol using an aminothiol-modified cation exchange resin as a catalyst, usually, a feed fluid containing a phenol compound and a ketone is continuously fed into a fixed-bed reactor filled with the resin. It is performed by distributing. Since the catalytic activity of the aminothiol-modified cation exchange resin gradually decreases, the catalyst is replaced once every several to twenty months. As described above, since the preparation of the aminothiol-modified cation exchange resin used as a catalyst is performed in a batch system, the catalyst is usually prepared and stored little by little in preparation for replacement. However, according to the study of the present inventors, it has been found that when stored in water, the modification rate of the resin decreases, and that one half of the cause is due to the aminothiol compound detaching from the resin during storage. did. When the aminothiol compound is desorbed from the catalyst adjusted to a predetermined modification rate to lower the modification rate, the catalyst does not exhibit the expected performance. Accordingly, an object of the present invention is to provide a method for suppressing elimination of an aminothiol compound when storing an aminothiol-modified cation exchange resin in water.
【０００３】[0003]
【課題を解決するための手段】本発明によれば、スルホ
ン酸基の一部をアミノチオール化合物で変性したスルホ
ン酸型陽イオン交換樹脂を、ｐＨ２〜７の水中に保存す
ることにより、保存中におけるアミノチオール化合物の
脱離を低減させることができる。According to the present invention, a sulfonic acid type cation exchange resin in which a part of sulfonic acid groups is modified with an aminothiol compound is stored in water having a pH of 2 to 7 so that the sulfonic acid type cation exchange resin can be stored. Elimination of the aminothiol compound can be reduced.
【０００４】[0004]
【発明の実施の形態】本発明でスルホン酸型陽イオン交
換樹脂の変性に用いるアミノチオール化合物としては、
２−アミノエタンチオールその他のアミノアルキルチオ
ールや、２−（４−ピリジル）エタンチオールその他の
ω−ピリジルアルカンチオールをはじめ、従来からこの
用途に用いる得ることが知られている任意のものを用い
ることができる。スルホン酸型陽イオン交換樹脂として
は、最も一般的なスチレン−ジビニルベンゼン共重合体
を濃硫酸などのスルホン化剤でスルホン化したものを用
いればよい。樹脂はゲル型でもポーラス型でもよい。所
望ならばフェノール−ホルムアルデヒド共重合体のスル
ホン化物を用いることもできる。スルホン酸型陽イオン
交換樹脂の交換容量は通常０．５〜６ｍｅｑ／ｇである
が、交換容量の大きいものを用いるのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The aminothiol compound used for modifying the sulfonic acid type cation exchange resin in the present invention includes:
Use any known amino acid thiol, such as 2-aminoethanethiol or other aminoalkyl thiol, or 2- (4-pyridyl) ethanethiol or other ω-pyridylalkanethiol, which can be used for this purpose. Can be. As the sulfonic acid type cation exchange resin, a resin obtained by sulfonating the most common styrene-divinylbenzene copolymer with a sulfonating agent such as concentrated sulfuric acid may be used. The resin may be a gel type or a porous type. If desired, a sulfonated phenol-formaldehyde copolymer can be used. The exchange capacity of the sulfonic acid type cation exchange resin is usually 0.5 to 6 meq / g, but it is preferable to use one having a large exchange capacity.
【０００５】スルホン酸型陽イオン交換樹脂の変性は、
先ず市場で入手したスルホン酸型陽イオン交換樹脂（ナ
トリウム型）を、希塩酸又は希硫酸で処理して遊離型に
転換する。十分に水洗して酸を除去したのち、これを計
算量のアミノチオール化合物を含む溶液で処理して、ス
ルホン酸基の一部、通常は１０〜４０％をアミノチオー
ル化合物で変性する。スルホン酸型陽イオン交換樹脂が
均一に変性されるように、アミノチオール化合物はスル
ホン酸型陽イオン交換樹脂と樹脂全体に亘って均一に接
触させるのが好ましい。次いで水洗して残存しているア
ミノチオール化合物を除去することにより、ビスフェノ
ール製造用触媒として好適なアミノチオール変性陽イオ
ン交換樹脂が得られる。The sulfonic acid type cation exchange resin is modified by
First, a commercially available sulfonic acid type cation exchange resin (sodium type) is treated with dilute hydrochloric acid or dilute sulfuric acid to be converted to a free type. After sufficient washing with water to remove the acid, it is treated with a solution containing a calculated amount of aminothiol compound to modify part of the sulfonic acid groups, usually 10 to 40%, with the aminothiol compound. It is preferable that the aminothiol compound is uniformly contacted with the sulfonic acid type cation exchange resin over the entire resin so that the sulfonic acid type cation exchange resin is uniformly modified. Then, by washing with water to remove the remaining aminothiol compound, an aminothiol-modified cation exchange resin suitable as a bisphenol production catalyst is obtained.
【０００６】本発明ではこのアミノチオール変性陽イオ
ン交換樹脂をｐＨ２〜７の水中に保存する。ｐＨが２よ
りも小さい水中に保存したのでは、保存中にアミノチオ
ール化合物が脱離してくる。これはスルホン酸基と結合
しているアミノチオール化合物は、解離平衡に基づき一
部が解離して水中に移るが、水のｐＨが２よりも小さい
と、水中に移ったアミノチオール化合物が酸と塩を形成
するので、樹脂からのアミノチオール化合物の解離が促
進されるためと考えられる。また水のｐＨが７よりも大
きくても、スルホン酸基と結合しているアミノチオール
化合物は、水中のアルカリにより置換されて樹脂から脱
離する。従ってアミノチオール変性陽イオン交換樹脂の
保存に際しては、ｐＨ２〜７の水を用いると共に、保存
中に樹脂から酸が溶出して水のｐＨが２よりも小さくな
らないようにする必要がある。そのためにはアミノチオ
ール化合物で変性する前に樹脂を十分に洗浄して含まれ
ている酸を低減させておくのが好ましい。また、長期の
保存に際しては保存中に水のｐＨを測定して、ｐＨが低
下している場合には水を取換えるべきである。なお、水
中の溶存酸素もアミノチオール変性陽イオン交換樹脂と
反応して樹脂の変性率を低下させるので、樹脂は容器に
充満させ、かつ容器を密封して保存するのが好ましい。
容器に樹脂を充満させることにより樹脂に対する水の比
率、従って樹脂に結合しているアミノチオール化合物に
対する水中の溶存酸素の比率を低下させて溶存酸素の影
響を緩和することができ、かつ密封することにより外部
からの酸素の補給を遮断することができる。好ましくは
窒素ガスによる曝気などにより溶存酸素を除去した水を
用いて保存する。また保存温度が高いとアミノチオール
化合物が脱離しやすいので、保存は室温ないしはそれ以
下の低温で行うのが好ましい。In the present invention, the aminothiol-modified cation exchange resin is stored in water having a pH of 2 to 7. When stored in water having a pH of less than 2, the aminothiol compound is released during storage. This is because the aminothiol compound bound to the sulfonic acid group is partially dissociated based on the dissociation equilibrium and moves into the water, but when the pH of the water is smaller than 2, the aminothiol compound transferred into the water is converted into an acid. It is considered that the formation of a salt promotes the dissociation of the aminothiol compound from the resin. Even when the pH of water is higher than 7, the aminothiol compound bonded to the sulfonic acid group is displaced by the alkali in the water and is eliminated from the resin. Therefore, when storing the aminothiol-modified cation exchange resin, it is necessary to use water having a pH of 2 to 7 and to prevent the acid from being eluted from the resin during the storage and the pH of the water to be lower than 2. For this purpose, it is preferable to sufficiently wash the resin before denaturation with the aminothiol compound to reduce the contained acid. In addition, during long-term storage, the pH of water should be measured during storage, and if the pH has dropped, the water should be replaced. Since dissolved oxygen in water also reacts with the aminothiol-modified cation exchange resin to lower the denaturation rate of the resin, the resin is preferably filled in a container, and the container is preferably sealed and stored.
Filling the container with resin can reduce the ratio of water to resin, and thus the ratio of dissolved oxygen in water to aminothiol compounds bound to the resin, to mitigate the effects of dissolved oxygen and seal. Thus, external supply of oxygen can be cut off. Preferably, it is stored using water from which dissolved oxygen has been removed by aeration with nitrogen gas. In addition, when the storage temperature is high, the aminothiol compound is easily desorbed, so that the storage is preferably performed at room temperature or lower temperature.
【０００７】[0007]
【実施例】以下に実施例により本発明を更に具体的に説
明する。 実施例１〜２及び比較例１ スルホン酸型陽イオン交換樹脂（ダイヤイオンＳＫ１０
４、ダイヤイオンは三菱化学社の登録商標）を希塩酸で
処理して遊離型とし、十分に水洗した。これを交換容量
の１８％に相当する２−（４−ピリジル）エタンチオー
ルを含む水溶液で処理して部分的に変性したのち水洗
し、２−（４−ピリジル）エタンチオールで変性したス
ルホン酸型陽イオン交換樹脂を得た。内容積２５０ｍｌ
のポリエチレン製のびん型の容器に、上記で調製した２
−（４−ピリジル）エタンチオール変性陽イオン交換樹
脂３０ｇ（湿量基準）を入れ、純水に硫酸を添加して酸
性とした水を加えて液封し、密栓して室温（約２３℃）
で９０日間保存したのち、水のｐＨと溶解している窒素
化合物を測定した。結果を表１に示す。なお、ｐＨの測
定は室温で行った。また窒素化合物の測定は全窒素計で
行った。The present invention will be described more specifically with reference to the following examples. Examples 1 and 2 and Comparative Example 1 Sulfonic acid type cation exchange resin (Diaion SK10
4. Diaion (registered trademark of Mitsubishi Chemical Co., Ltd.) was treated with dilute hydrochloric acid to form a free form, and washed thoroughly with water. This was treated with an aqueous solution containing 2- (4-pyridyl) ethanethiol corresponding to 18% of the exchange capacity, partially modified, washed with water, and then modified with 2- (4-pyridyl) ethanethiol as a sulfonic acid type. A cation exchange resin was obtained. Internal volume 250ml
2 prepared above in a polyethylene bottle type container
-(4-Pyridyl) ethanethiol-modified cation exchange resin (30 g, based on wet weight) was added, sulfuric acid was added to pure water, acidified water was added, the solution was sealed, sealed, and sealed at room temperature (about 23 ° C).
After storing for 90 days, the pH of water and the dissolved nitrogen compounds were measured. Table 1 shows the results. The pH was measured at room temperature. The measurement of the nitrogen compound was performed with a total nitrogen meter.
【０００８】[0008]
【表１】 [Table 1]
【０００９】比較例２ 変性剤として２−（４−ピリジル）エタンチオールの代
りに２−アミノエタンチオールを用いた以外は、実施例
１と全く同様にして２−アミノエタンチオールで１８％
変性したスルホン酸型陽イオン交換樹脂を調製した。こ
の変性陽イオン交換樹脂を用いた以外は比較例１と全く
同様にして保存試験を行ったところ、水中には７０ｐｐ
ｍの窒素が溶解していた。Comparative Example 2 Except that 2-aminoethanethiol was used in place of 2- (4-pyridyl) ethanethiol as a modifier, 18% 2-aminoethanethiol was used in exactly the same manner as in Example 1.
A modified sulfonic acid type cation exchange resin was prepared. A storage test was performed in exactly the same manner as in Comparative Example 1 except that this modified cation exchange resin was used.
m of nitrogen had dissolved.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA15 BA21A BA21B BA24A BA24B BE21A BE21B BE38A BE38B CB25 CB62 CB70 DA05 ED05 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA15 BA21A BA21B BA24A BA24B BE21A BE21B BE38A BE38B CB25 CB62 CB70 DA05 ED05
Claims (2)
合物で変性した変性スルホン酸型陽イオン交換樹脂を、
ｐＨ２〜７の水中に保存することを特徴とするアミノチ
オール変性陽イオン交換樹脂の保存方法。1. A modified sulfonic acid type cation exchange resin in which a part of sulfonic acid groups is modified with an aminothiol compound,
A method for storing an aminothiol-modified cation exchange resin, which is stored in water having a pH of 2 to 7.
ルカンチオールであり、スルホン酸型陽イオン交換樹脂
のスルホン酸基の１０〜４０％が変性されていることを
特徴とする請求項１記載のアミノチオール変性陽イオン
交換樹脂の保存方法。2. The aminothiol compound according to claim 1, wherein the aminothiol compound is ω-pyridylalkanethiol, and 10 to 40% of the sulfonic acid groups of the sulfonic acid type cation exchange resin are modified. How to store the modified cation exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000193699A JP3937694B2 (en) | 2000-06-28 | 2000-06-28 | Storage method of aminothiol-modified cation exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000193699A JP3937694B2 (en) | 2000-06-28 | 2000-06-28 | Storage method of aminothiol-modified cation exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002001134A true JP2002001134A (en) | 2002-01-08 |
| JP3937694B2 JP3937694B2 (en) | 2007-06-27 |
Family
ID=18692643
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|---|---|---|---|
| JP2000193699A Expired - Lifetime JP3937694B2 (en) | 2000-06-28 | 2000-06-28 | Storage method of aminothiol-modified cation exchange resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002045855A1 (en) * | 2000-12-07 | 2002-06-13 | Mitsubishi Chemical Corporation | Method of storing aminothiol-modified sulfonic acid type cation-exchange resin |
| JP2008528276A (en) * | 2005-01-28 | 2008-07-31 | ダウ グローバル テクノロジーズ インコーポレイティド | Methods for stabilizing cation exchange resins prior to use as acid catalysts and the use of stabilized cation exchange resins in chemical processes |
| KR100997155B1 (en) | 2009-05-27 | 2010-11-30 | 삼성전자주식회사 | OFDM transmitter capable of adjusting size of PN and inserting adjusted PN into OFDM symbol |
| WO2013101493A1 (en) * | 2011-12-28 | 2013-07-04 | Rohm And Haas Company | Process of producing and use of a treated, promoted ion exchange resin catalyst |
-
2000
- 2000-06-28 JP JP2000193699A patent/JP3937694B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002045855A1 (en) * | 2000-12-07 | 2002-06-13 | Mitsubishi Chemical Corporation | Method of storing aminothiol-modified sulfonic acid type cation-exchange resin |
| US6696385B2 (en) | 2000-12-07 | 2004-02-24 | Mitsubishi Chemical Corporation | Method of preserving sulfonic acid-type cation-exchange resin modified with thiol-containing amine compound |
| JP2008528276A (en) * | 2005-01-28 | 2008-07-31 | ダウ グローバル テクノロジーズ インコーポレイティド | Methods for stabilizing cation exchange resins prior to use as acid catalysts and the use of stabilized cation exchange resins in chemical processes |
| JP2013136604A (en) * | 2005-01-28 | 2013-07-11 | Dow Global Technologies Llc | Method for stabilizing cation exchange resin prior to use as acid catalyst and use of stabilized cation exchange resin in chemical process |
| KR100997155B1 (en) | 2009-05-27 | 2010-11-30 | 삼성전자주식회사 | OFDM transmitter capable of adjusting size of PN and inserting adjusted PN into OFDM symbol |
| WO2013101493A1 (en) * | 2011-12-28 | 2013-07-04 | Rohm And Haas Company | Process of producing and use of a treated, promoted ion exchange resin catalyst |
| CN103987459A (en) * | 2011-12-28 | 2014-08-13 | 罗门哈斯公司 | Process of producing and use of a treated, promoted ion exchange resin catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3937694B2 (en) | 2007-06-27 |
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