JP2000254523A - Method for preparing catalyst for producing bisphenol - Google Patents
Method for preparing catalyst for producing bisphenolInfo
- Publication number
- JP2000254523A JP2000254523A JP11061727A JP6172799A JP2000254523A JP 2000254523 A JP2000254523 A JP 2000254523A JP 11061727 A JP11061727 A JP 11061727A JP 6172799 A JP6172799 A JP 6172799A JP 2000254523 A JP2000254523 A JP 2000254523A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- cation exchange
- acidic cation
- nitrogen
- catalyst
- 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.)
- Pending
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ビスフェノール類
製造用触媒の調製方法に関し、さらに詳しくは、酸性陽
イオン交換樹脂を含窒素硫黄化合物で均一に中和してな
るビスフェノール類製造用触媒の調製方法に関する。The present invention relates to a method for preparing a catalyst for producing bisphenols, and more particularly, to a method for preparing a catalyst for producing bisphenols obtained by uniformly neutralizing an acidic cation exchange resin with a nitrogen-containing sulfur compound. About the method.
【０００２】[0002]
【従来の技術】ビスフェノールＡ〔２，２−ビス（４−
ヒドロキシフェニル）プロパン〕は、ポリカーボネート
樹脂やポリアリレート樹脂などのエンジニアリングプラ
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。このビスフェノールＡをは
じめとするビスフェノール類は、酸性陽イオン交換樹脂
を触媒とし、フェ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、
ビスフェノールＡを例に採れば、異性体である２−（２
−ヒドロキシフェニル）−２−（４−ヒドロキシフェニ
ル）プロパンの副生を抑えるために、酸性陽イオン交換
樹脂の一部を含窒素硫黄化合物で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。2. Description of the Related Art Bisphenol A [2,2-bis (4-
Hydroxyphenyl) propane] is known to be an important compound as a raw material for engineering plastics such as polycarbonate resins and polyarylate resins, or epoxy resins, and in recent years, its demand has tended to increase. It is known that bisphenols such as bisphenol A are produced by reacting a phenol with a carbonyl compound using an acidic cation exchange resin as a catalyst. In that case,
Taking bisphenol A as an example, the isomer 2- (2
It is also known to use a catalyst obtained by neutralizing a part of an acidic cation exchange resin with a nitrogen-containing sulfur compound in order to suppress the by-product of (-hydroxyphenyl) -2- (4-hydroxyphenyl) propane. Therefore, various methods have been attempted as neutralization methods.
【０００３】例えば、特開昭５３−１４６８０号報に
は、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
腐食の問題があるだけでなく、また、循環する液体の空
間速度が非常に速く実際的ではない。特開平６−３１９
９８１号公報には、触媒調製工程と触媒充填工程を順次
繰り返し行う方法が開示されているが、装置が複雑で煩
雑である。また、特開平８−４０９６１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、芳香族カルボン酸類は腐食
の問題はないが、酸を添加しているため、溶液とイオン
交換樹脂中に平衡が生じ、中和剤の全てを樹脂の中和に
利用することはできないので、中和剤に無駄が生じる。For example, Japanese Patent Application Laid-Open No. 53-14680 discloses a method of circulating a liquid containing hydrochloric acid in a fixed resin bed. However, the use of hydrochloric acid not only has the problem of corrosion of the equipment, but also the space velocity of the circulating liquid is too fast to be practical. JP-A-6-319
No. 981 discloses a method in which a catalyst preparation step and a catalyst filling step are sequentially repeated, but the apparatus is complicated and complicated. JP-A-8-40961 discloses a method in which aromatic sulfonic acids are added to a nitrogen-containing sulfur compound as a neutralizing agent. Because of the addition, an equilibrium occurs between the solution and the ion exchange resin, and the neutralizing agent is wasted because not all of the neutralizing agent can be used for neutralizing the resin.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記観点か
らなされたもので、装置腐食の問題がなく、簡便に効率
よく酸性陽イオン交換樹脂を含窒素硫黄化合物で均一に
中和することができるビスフェノール類製造用触媒の調
製方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above point of view, and has no problem of equipment corrosion, and can easily and efficiently neutralize an acidic cation exchange resin uniformly with a nitrogen-containing sulfur compound. The present invention provides a method for preparing a catalyst for producing bisphenols.
【０００５】[0005]
【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、反応器に酸性陽イオン交換樹脂が充填され
た状態で、含窒素硫黄化合物の水溶液を反応器内に装入
しながら、又は装入した後、反応器下部より気泡を流通
させることにより、上記発明の目的を効果的に達成しう
ることを見出し本発明を完成したものである。Means for Solving the Problems As a result of intensive studies, the present inventors have charged an aqueous solution of a nitrogen-containing sulfur compound into a reactor in a state where the reactor is filled with an acidic cation exchange resin. It has been found that the object of the present invention can be effectively achieved by circulating air bubbles from the lower part of the reactor while or after charging, and the present invention has been completed.
【０００６】すなわち、本発明は、酸性陽イオン交換樹
脂を含窒素硫黄化合物で部分的に中和してなるビスフェ
ノール類の製造用触媒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、含窒素硫黄化合物の水溶
液を装入しながら、又は装入した後、反応器下部から気
泡を流通させて酸性陽イオン交換樹脂を均一に中和する
ことを特徴とするビスフェノール類製造用触媒の調製方
法である。That is, the present invention relates to a method for preparing a catalyst for producing bisphenols, which is obtained by partially neutralizing an acidic cation exchange resin with a nitrogen-containing sulfur compound. While charging an aqueous solution of a nitrogen-containing sulfur compound, or after charging, a bubble is circulated from the lower part of the reactor to uniformly neutralize the acidic cation exchange resin. It is a preparation method.
【０００７】[0007]
【発明の実施の形態】以下に、本発明について詳細に説
明する。本発明において、ビスフェノール類は、フェノ
ール類とカルボニル化合物とを反応させて製造される。
フェノール類は、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、フェノール、ｏ−
クレゾール、ｍ−クレゾール、ｏ−ｔｅｒｔ−ブチルフ
ェノール、２，６−キシレノール、２，６−ジ−ｔｅｒ
ｔ−ブチルフェノール等のアルキルフェノールやｏ−ク
ロロフェノール、ｍ−クロロフェノール、２，６−ジク
ロロフェノール等のハロゲン化フェノールを挙げること
ができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, bisphenols are produced by reacting phenols with carbonyl compounds.
Phenols need not have a substituent at the para-position to the hydroxyl group. Specifically, phenol, o-
Cresol, m-cresol, o-tert-butylphenol, 2,6-xylenol, 2,6-di-ter
Examples thereof include alkylphenols such as t-butylphenol and halogenated phenols such as o-chlorophenol, m-chlorophenol and 2,6-dichlorophenol.
【０００８】カルボニル化合物としては、具体的には、
アセトン，メチルエチルケトン，メチルイソブチルケト
ン，メチル−ｎ−プロピルケトン，アセトフェノン，シ
クロヘキサノン等のケトン類やホルマリン，アセトアル
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。好適には、本発明は、アセトンとフェノー
ルを原料とするビスフェノールＡの製造に適用できる。As the carbonyl compound, specifically,
Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-propyl ketone, acetophenone and cyclohexanone, and aldehydes such as formalin, acetaldehyde and benzaldehyde. Preferably, the present invention is applicable to the production of bisphenol A from acetone and phenol.
【０００９】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−ジビニルベンゼン共重合体系，パー
フルオロエチレン共重合体系，フェノール−ホルムアル
デヒド重合体系等があるが、スチレン−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、反応器に充填し固定床を形成させる。The acidic cation exchange resin used as a catalyst is preferably a sulfonic acid-based resin, and the base resin is a styrene-divinylbenzene copolymer, a perfluoroethylene copolymer, a phenol-formaldehyde polymer, or the like. However, a styrene-divinylbenzene copolymer system is preferred. These resins can be used in either a gel type or a porous type.
A relatively low value of about 8% is preferable. The acidic cation exchange resin is charged into a reactor to form a fixed bed.
【００１０】反応器に酸性陽イオン交換樹脂を充填した
後、必要に応じ反応器出口の洗浄廃水のｐＨが６以上に
なるまで水洗を行った方がよい。この反応器へ前記の原
料を装入して連続的に反応を行うが、反応を開始する前
に、含窒素硫黄化合物の水溶液を装入しながら、又は装
入した後、反応器下部から気泡を流通させて酸性陽イオ
ン交換樹脂を均一に中和する。[0010] After filling the reactor with the acidic cation exchange resin, it is preferable to wash with water until the pH of the washing wastewater at the outlet of the reactor becomes 6 or more, if necessary. The reaction is continuously carried out by charging the above-mentioned raw materials into this reactor. Before starting the reaction, while the aqueous solution of the nitrogen-containing sulfur compound is being charged, or after charging, air bubbles are generated from the lower portion of the reactor. To neutralize the acidic cation exchange resin uniformly.
【００１１】上記の含窒素硫黄化合物としては、例え
ば、２−メルカプトエチルアミン、３−メルカプトブチ
ルアミン等のメルカプトアルキルアミン類、２，２−ジ
メチルチアゾリジン、２−メチル−２−エチルチアゾリ
ジン、シクロアルキルチアゾリジン、２−メチル−２−
フェニルチアゾリジン、３−メチルチアゾリジン等のチ
アゾリジン類、１，４−アミノチオフェノール等のアミ
ノチオフェノール類、３−メルカプトメチルピリジン、
３−メルカプトエチルピリジン、４−メルカプトエチル
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
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２〜５０モル％、好ましくは５〜３０モル％であ
る。Examples of the nitrogen-containing sulfur compound include mercaptoalkylamines such as 2-mercaptoethylamine and 3-mercaptobutylamine, 2,2-dimethylthiazolidine, 2-methyl-2-ethylthiazolidine, cycloalkylthiazolidine, 2-methyl-2-
Phenylthiazolidine, thiazolidine such as 3-methylthiazolidine, aminothiophenols such as 1,4-aminothiophenol, 3-mercaptomethylpyridine,
Mercaptoalkylpyridines such as 3-mercaptoethylpyridine and 4-mercaptoethylpyridine can be exemplified, and among them, mercaptoalkylamines and thiazolidines are preferable. The amount of the nitrogen-containing sulfur compound to be used is 2 to 50 mol%, preferably 5 to 30 mol%, based on the sulfonic acid groups in the acidic cation exchange resin.
【００１２】中和を行う温度については、室温でもよい
し、あるいは３０〜１００℃に加温してもよい。１００
℃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。反応器下部からの気泡の流通
は、空気や窒素、アルゴンなどの不活性ガスを流通させ
ることによって行えばよいが、不活性ガスが好ましい。
気泡の流通時間、流通速度は特に限定されないが、所望
の中和率になるように適宜選択すればよい。その所望の
中和率は、２〜５０％、好ましくは５〜３０％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。上記の気泡の流通の開始時期
は、含窒素硫黄化合物の水溶液が反応器出口から流出す
る前であればよい。The temperature at which the neutralization is performed may be room temperature or may be heated to 30 to 100 ° C. 100
When the temperature exceeds ℃, the sulfonic acid of the ion exchange resin is strongly desorbed, which is not preferable. The flow of air bubbles from the lower part of the reactor may be performed by flowing an inert gas such as air, nitrogen, or argon, but an inert gas is preferable.
The flow time and flow rate of the bubbles are not particularly limited, but may be appropriately selected so as to obtain a desired neutralization ratio. The desired degree of neutralization is 2 to 50%, preferably 5 to 30%.
If the neutralization ratio is too low or too high, sufficient catalytic activity cannot be exhibited. The start time of the flow of the bubbles may be before the aqueous solution of the nitrogen-containing sulfur compound flows out of the reactor outlet.
【００１３】[0013]
【実施例】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。 〔実施例１〕底部にガラスフィルター、液抜き出し用ラ
イン及びコックを備えたガラスの二重容器（内容積６０
０ｃｃ）に水膨潤状態の酸性陽イオン交換樹脂（三菱化
学社製、商品名：ダイヤイオンＳＫ−１０４）２００ｃ
ｃを充填し（樹脂層は約８０ｍｍ）、容器出口の洗浄廃
水のｐＨが６以上になるまで水で流通洗浄した。次い
で、容器に水２００ｃｃを加え、さらに２−メルカプト
エチルアミン３．６ｇを水１００ｃｃに溶解させた水溶
液を一気に加えた後、直ちに容器下部から窒素を１５０
ｃｃ／分で２時間流通させた。その後、ろ過により水を
ろ別し、イオン交換樹脂層上部と下部から樹脂をサンプ
リングし（図１参照）、中和率を求めた。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。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [Example 1] A glass double container having a glass filter, a liquid extraction line and a cock at the bottom (with an inner volume of 60
Water swelling acidic cation exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name: Diaion SK-104) 200c
c (the resin layer is about 80 mm), and washed with water until the pH of the washing wastewater at the outlet of the container becomes 6 or more. Next, 200 cc of water was added to the container, and an aqueous solution in which 3.6 g of 2-mercaptoethylamine was dissolved in 100 cc of water was added all at once.
Flowed at cc / min for 2 hours. Thereafter, water was separated by filtration, and the resin was sampled from the upper and lower portions of the ion-exchange resin layer (see FIG. 1) to determine the neutralization ratio. Table 1 shows the results. The neutralization ratio was determined by the following equation.
【００１４】[0014]
【数１】 (Equation 1)
【００１５】（上式で、酸当量は水酸化ナトリウム水溶
液を用いて滴定法で測定した。） 〔比較例１〕実施例１において、容器下部から窒素を流
通させない点以外は同様に実施し樹脂の中和率を求め
た。その結果を第１表に示す。(In the above formula, the acid equivalent was measured by a titration method using an aqueous solution of sodium hydroxide.) [Comparative Example 1] A resin was prepared in the same manner as in Example 1 except that nitrogen was not allowed to flow from the lower part of the vessel. Was determined. Table 1 shows the results.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明によれば、装置腐食の問題がな
く、簡便に効率よく酸性陽イオン交換樹脂を含窒素硫黄
化合物で均一に中和することができ、ビスフェノール類
製造用触媒として有効に利用することができる。According to the present invention, the acidic cation exchange resin can be simply and efficiently neutralized uniformly and efficiently with a nitrogen-containing sulfur compound without the problem of equipment corrosion, and is effectively used as a catalyst for producing bisphenols. Can be used.
【図１】 イオン交換樹脂層のサンプリング箇所の説明
図である。FIG. 1 is an explanatory diagram of a sampling location of an ion exchange resin layer.
１：イオン交換樹脂層 ２：イオン交換樹脂層の上部中央 ３：イオン交換樹脂層の下部中央 ４：イオン交換樹脂層の下部端 1: ion exchange resin layer 2: upper center of ion exchange resin layer 3: lower center of ion exchange resin layer 4: lower end of ion exchange resin layer
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA08 BA24A BA24B CB25 FB26 4H006 AC21 BA72 FC52 FE13 4H039 CA11 CA12 CA19 CD10 CD40 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA08 BA24A BA24B CB25 FB26 4H006 AC21 BA72 FC52 FE13 4H039 CA11 CA12 CA19 CD10 CD40
Claims (4)
物で部分的に中和してなるビスフェノール類の製造用触
媒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、含窒素硫黄化合物の水溶液を装入しながら、
又は装入した後、反応器下部から気泡を流通させて酸性
陽イオン交換樹脂を均一に中和することを特徴とするビ
スフェノール類製造用触媒の調製方法。1. A process for preparing a catalyst for producing bisphenols, comprising partially neutralizing an acidic cation exchange resin with a nitrogen-containing sulfur compound, wherein a reactor is filled with the acid cation exchange resin, and the nitrogen-containing sulfur While loading the aqueous solution of the compound,
Alternatively, a method for preparing a catalyst for producing bisphenols, characterized in that bubbles are passed from the lower part of the reactor after charging, thereby uniformly neutralizing the acidic cation exchange resin.
陽イオン交換樹脂である請求項１記載のビスフェノール
類製造用触媒の調製方法。2. The method for preparing a catalyst for producing bisphenols according to claim 1, wherein the acidic cation exchange resin is a sulfonic acid type cation exchange resin.
ルアミン類又はチアゾリジン類である請求項１又は２に
記載のビスフェノール類製造用触媒の調製方法。3. The method for preparing a catalyst for producing bisphenols according to claim 1, wherein the nitrogen-containing sulfur compound is a mercaptoalkylamine or a thiazolidine.
ある請求項１〜３のいずれかに記載のビスフェノール類
製造用酸性陽イオン交換樹脂の調製方法。4. The method for preparing an acidic cation exchange resin for producing a bisphenol according to claim 1, wherein the bisphenol is bisphenol A.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11061727A JP2000254523A (en) | 1999-03-09 | 1999-03-09 | Method for preparing catalyst for producing bisphenol |
| PCT/JP2000/001399 WO2000053315A1 (en) | 1999-03-09 | 2000-03-08 | Process for preparing catalyst for use in bisphenol production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11061727A JP2000254523A (en) | 1999-03-09 | 1999-03-09 | Method for preparing catalyst for producing bisphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000254523A true JP2000254523A (en) | 2000-09-19 |
Family
ID=13179547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11061727A Pending JP2000254523A (en) | 1999-03-09 | 1999-03-09 | Method for preparing catalyst for producing bisphenol |
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| JP (1) | JP2000254523A (en) |
| WO (1) | WO2000053315A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042154A1 (en) * | 2003-11-04 | 2005-05-12 | Idemitsu Kosan Co., Ltd. | Method of preparing modified catalyst for bisphenol a production |
| JP2007111629A (en) * | 2005-10-20 | 2007-05-10 | Idemitsu Kosan Co Ltd | Extraction method of used ion-exchange resin catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002316962A (en) * | 2001-04-17 | 2002-10-31 | Idemitsu Petrochem Co Ltd | Method for producing bisphenol a |
| ES2359476T3 (en) * | 2007-06-14 | 2011-05-23 | Dow Global Technologies Inc. | PREPARATION OF CATALYST FOR THE PRODUCTION OF BISPHENOLS. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3217598B2 (en) * | 1994-08-02 | 2001-10-09 | 新日鐵化学株式会社 | Method for preparing fixed bed of acidic cation exchange resin |
| CN1038395C (en) * | 1994-10-25 | 1998-05-20 | 中国石油化工总公司 | Ion exchange resin catalyzer for synthesising bisphenol and preparation thereof |
| DE69616232T2 (en) * | 1995-09-29 | 2002-06-27 | Gen Electric | Process for the preparation of bisphenol compounds with simultaneous drainage |
-
1999
- 1999-03-09 JP JP11061727A patent/JP2000254523A/en active Pending
-
2000
- 2000-03-08 WO PCT/JP2000/001399 patent/WO2000053315A1/en active Search and Examination
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042154A1 (en) * | 2003-11-04 | 2005-05-12 | Idemitsu Kosan Co., Ltd. | Method of preparing modified catalyst for bisphenol a production |
| JP2007111629A (en) * | 2005-10-20 | 2007-05-10 | Idemitsu Kosan Co Ltd | Extraction method of used ion-exchange resin catalyst |
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| Publication number | Publication date |
|---|---|
| WO2000053315A1 (en) | 2000-09-14 |
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