JPH05117194A - Method for producing high-quality bisphenol A / phenol crystal adduct - Google Patents
Method for producing high-quality bisphenol A / phenol crystal adductInfo
- Publication number
- JPH05117194A JPH05117194A JP3306524A JP30652491A JPH05117194A JP H05117194 A JPH05117194 A JP H05117194A JP 3306524 A JP3306524 A JP 3306524A JP 30652491 A JP30652491 A JP 30652491A JP H05117194 A JPH05117194 A JP H05117194A
- Authority
- JP
- Japan
- Prior art keywords
- crystal adduct
- phenol
- stage
- solid
- liquid separation
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】 （修正有）
【目的】 複数の晶析工程を含む、高品位結晶アダクト
の経済的な製造方法の提供。
【構成】 第１〜第ｎ−１段の各段の晶析工程Ａ−１〜
２の晶析生成物を固液分離Ｂ−１〜２し、得た結晶アダ
クトをそのまま又は洗浄液で洗浄した後、フェノ−ル溶
液で再溶解Ｃ−１〜２して次段の晶析工程に供給し、か
つ第ｎ段の晶析工程Ａ−３の晶析生成物を固液分離Ｂ−
３し、得た結晶アダクトを洗浄液で洗浄して高純度の結
晶アダクトを得る方法において、第ｎ番の結晶アダクト
の洗浄液に精製フェノ−ルを用い、第ｎ−１段で得た結
晶アダクトの再溶解用フェノ−ル溶液に第ｎ段からの結
晶アダクトの洗浄排液又は母液を用い、第ｎ−１段の固
液分離工程Ａ−２で得た結晶アダクトの洗浄液に第ｎ段
からの母液又は結晶アダクトの洗浄排液を用い、第１〜
ｎ−１段の各段の結晶アダクト再溶解用フェノ−ル溶液
中の不純物濃度と結晶アダクト洗浄液中の不純物濃度を
各々次段よりも高くする。
(57) [Summary] (Modified) [Purpose] To provide an economical manufacturing method of a high-quality crystal adduct including a plurality of crystallization steps. [Structure] Crystallization steps A-1 to 1-nth stages
The crystallized product of No. 2 is subjected to solid-liquid separation B-1 and B-2, and the obtained crystal adduct is washed as it is or with a washing liquid, and then redissolved in a phenol solution C-1 and C-2 to perform the next crystallization step. And the crystallization product of the nth stage crystallization step A-3 is subjected to solid-liquid separation B-.
In the method for obtaining a high-purity crystal adduct by washing the obtained crystal adduct with a washing solution, a purified phenol is used as a washing solution for the n-th crystal adduct, and the crystal adduct obtained in the (n-1) th stage is used. The cleaning effluent or mother liquor of the crystal adduct from the nth stage was used as the phenol solution for redissolution, and the cleaning liquid of the crystal adduct obtained in the solid-liquid separation step A-2 of the nth stage was used as Using the cleaning effluent of mother liquor or crystal adduct,
The impurity concentration in the crystal adduct re-dissolving phenol solution and the impurity concentration in the crystal adduct cleaning solution in each of the n-1 stages are made higher than in the next stage.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、色相にすぐれかつ着色
を生じにくい高品位ビスフェノ−ルＡ．フェノ−ル結晶
アダクトの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-quality bisphenol A.A. The present invention relates to a method for producing a phenol crystal adduct.
【０００２】[0002]
【従来技術及びその問題点】ビスフェノ−ルＡ〔２，２
−ビス（４′ヒドロキシフェニル）プロパン〕を製造す
るために、酸触媒の存在下、過剰のフェノ−ルにアセト
ンを反応させることは知られている。また、この反応生
成物から高純度ビスフェノ−ルＡを分離回収するため
に、反応生成物を晶析処理してビスフェノ−ルＡとフェ
ノ−ルとの結晶アダクト（以下、単に結晶アダクトとも
言う）を析出させ、得られた結晶アダクトからフェノ−
ルを除去することも知られている。（特公昭６６−２３
３３５号、特公昭５２−４２７９０号）。このようなビ
スフェノ−ルＡの製造方法において、製品として回収さ
れるビスフェノ−ルＡの色相は、その結晶アダクト自体
の色相に大きく依存することから、高品位結晶アダクト
の製造方法の開発が要望される。従来、高純度の結晶ア
ダクトを得るために、ビスフェノ−ルＡを含むフェノ−
ル溶液を晶析処理して得られた結晶アダクトスラリ−を
濾過処理し、分離された結晶アダクトを高純度フェノ−
ルで洗浄することは知られている。この場合、晶析工程
の数を増加することにより、純度の高められた製品結晶
アダクトを得ることができる。しかし、このような複数
の晶析工程を含む結晶アダクトの製造において、各晶析
工程で得られる結晶アダクト洗浄用の各洗浄液に高純度
のフェノ−ルを用いても、結晶アダクトの格別の高純度
化は達成されず、むしろ、その高純度フェノ−ルを大量
に得るためのコストが高くなるという問題がある。2. Description of the Related Art Bisphenol A [2, 2]
It is known to react excess phenol with acetone in the presence of an acid catalyst to produce -bis (4'hydroxyphenyl) propane]. In order to separate and recover high-purity bisphenol A from this reaction product, the reaction product is crystallized to form a crystal adduct of bisphenol A and phenol (hereinafter, also simply referred to as a crystal adduct). From the obtained crystal adduct.
It is also known to remove the le. (Japanese Patent Publication No. 66-23
335, Japanese Examined Patent Publication No. 52-42790). In such a method for producing bisphenol A, since the hue of bisphenol A recovered as a product largely depends on the hue of the crystal adduct itself, development of a method for producing a high-quality crystal adduct is desired. It Conventionally, in order to obtain a high-purity crystal adduct, a phenol containing bisphenol A is used.
The crystal adduct slurry obtained by crystallizing the solution is filtered, and the separated crystal adduct is treated with high-purity phenol.
It is known to wash with a le. In this case, by increasing the number of crystallization steps, a product crystal adduct with increased purity can be obtained. However, in the production of such a crystal adduct containing a plurality of crystallization steps, even if a high-purity phenol is used for each cleaning solution for cleaning the crystal adduct obtained in each crystallization step, the crystal adduct has a particularly high yield. Purification is not achieved, but rather there is a problem that the cost for obtaining a large amount of the high-purity phenol becomes high.
【０００３】[0003]
【発明が解しようとする課題】本発明は、複数の晶析工
程を含む、高品位結晶アダクトを経済的に製造する方法
を提供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for economically producing a high-quality crystal adduct, which comprises a plurality of crystallization steps.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、ビスフェノ−ルＡを
含むフェノ−ル溶液を、ｎ（ｎ≧２）段の晶析工程、ｎ
段の固液分離工程、少なくとも１段のビスフェノ−ルＡ
・フェノ−ル結晶アダクト洗浄工程及びｎ−１段の結晶
アダクト再溶解工程を含み、第１段目から第ｎ−１段目
の各段の晶析工程で得られた晶析生成物を固液分離し、
得られた結晶アダクトをそのままあるいは洗浄液で洗浄
した後、フェノ−ル溶解で再溶解して次段の晶析工程に
供給し、かつ第ｎ段目の晶析工程で得られた晶析生成物
を固液分離し、得られた結晶アダクト洗浄液で洗浄して
高純度の結晶アダクトを得る方法において、（ａ）第ｎ
段目の固液分離工程で得られた第ｎ番目の結晶アダクト
の洗浄液の少なくとも一部に、精製フェノ−ルを用いる
こと、（ｂ）少なくとも第ｎ−１段目の固液分離工程で
得られた結晶アダクトの再溶解用フェノ−ル溶液の少な
くとも一部に、第ｎ段目の固液分離工程で得られた結晶
アダクトの洗浄排液又は第ｎ段目の固液分離工程で得ら
れた母液を用いること、（ｃ）少なくとも第ｎ−１段目
の固液分離工程で得られた結晶アダクトの洗浄液の少な
くとも一部に、第ｎ段目の固液分離工程で得られた母液
又は第ｎ段目の固液分離工程で得られた結晶アダクトの
洗浄排液を用いること、（ｄ）第１段目から第ｎ−１段
目までの各段における結晶アダクト再溶解用フェノ−ル
溶液中の不純物濃度及び結晶アダクト洗浄液中の不純物
濃度が、いずれも次段における結晶アダクト再溶解用フ
ェノ−ル溶液中の不純物濃度及び結晶アダクト洗浄液中
の不純物濃度よりも高いこと、を特徴とするビスフェノ
−ルＡ・フェノ−ル結晶アダクトの製造方法が提供され
る。The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, a phenol solution containing bisphenol A is subjected to n (n ≧ 2) stages of crystallization step,
Solid-liquid separation step, at least one step of bisphenol A
-A crystallization product obtained in the crystallization step of each of the first to n-1th stages is solidified, including a phenol crystal adduct washing step and an n-1th stage crystal adduct redissolution step. Liquid separation,
The obtained crystal adduct is washed as it is or with a washing solution, then redissolved by phenol dissolution and supplied to the next crystallization step, and the crystallization product obtained in the nth crystallization step Solid-liquid separation and washing with the obtained crystal adduct washing liquid to obtain a high-purity crystal adduct,
Use of purified phenol in at least a part of the washing liquid for the n-th crystal adduct obtained in the solid-liquid separation step of the stage, (b) Obtained in the solid-liquid separation step of the (n-1) th stage At least a part of the re-dissolving phenol solution for the crystal adduct thus obtained was washed with the crystal adduct obtained in the n-th solid-liquid separation step or obtained in the n-th solid-liquid separation step. The mother liquor obtained in the n-th solid-liquid separation step, or (c) the mother liquor obtained in the n-th solid-liquid separation step, or Using the cleaning waste liquid of the crystal adduct obtained in the solid-liquid separation step of the n-th stage, (d) a phenol for re-dissolving the crystal adduct in each stage from the first stage to the (n-1) th stage The impurity concentration in the solution and the crystal adduct cleaning liquid are both Le A · phenol - - bisphenol characterized by high that, than the impurity concentration of the impurity concentration in the Le solution and crystal adduct in the washing liquid - crystalline adduct redissolved for phenol in stage manufacturing method of Le crystalline adduct is provided.
【０００５】次に、本発明を図面を参照して説明する。
図１は本発明の方法を実施する場合のフロ−シ−トの１
例を示す。図１において、Ａ−１、Ａ−２、Ａ−３は、
それぞれ、第１晶析工程、第２晶析工程、第３晶析工程
を示す。Ｂ−１、Ｂ−２、Ｂ−３は、それぞれ、第１固
液分離工程、第２固液分離工程、第３固液分離工程を示
す。Ｃ−１、Ｃ−２は、それぞれ、結晶アダクトの第１
再溶解工程、第２再溶解工程を示す。図１に示したフロ
−シ−トに従って結晶アダクトを製造する場合、その定
常状態のフロ−においては、晶析処理用原料液であるビ
スフェノ−ルＡを含むフェノ−ル溶液はライン１を通っ
て第１晶析工程Ａ−１に導入される。Next, the present invention will be described with reference to the drawings.
FIG. 1 is a flow chart for carrying out the method of the present invention.
Here is an example: In FIG. 1, A-1, A-2, and A-3 are
The first crystallization step, the second crystallization step, and the third crystallization step are shown respectively. B-1, B-2, and B-3 show a first solid-liquid separation step, a second solid-liquid separation step, and a third solid-liquid separation step, respectively. C-1 and C-2 are the first crystal adducts, respectively.
The redissolution step and the second redissolution step are shown. When the crystal adduct is produced according to the flow sheet shown in FIG. 1, in the steady state flow, the phenol solution containing bisphenol A as the raw material solution for crystallization treatment passes through line 1. Are introduced into the first crystallization step A-1.
【０００６】第１晶析工程Ａ−１で得られた晶析生成物
は、ライン２を通って第１固液分離工程Ｂ−１に導入さ
れ、ここで第１結晶アダクトＤ−１と第１母液Ｆ−１と
に分離され、第１母液Ｆ−１は、その中にフェノ−ル、
ビスフェノ−ルＡ等の有用成分を含むため、適当な処理
を施した後、フェノ−ルとアセトンとの反応工程へ循環
させる。第１晶析生成物から分離された第１結晶アダク
トは、次段の第２固液分離工程Ｂ−２で得られた第２母
液Ｆ−２で洗浄され、この洗浄で得られた第１洗浄排液
Ｅ−１は、フェノールとアセトンとの反応工程へ循環さ
れる。前記のように、第２母液Ｆ−２で洗浄された第１
結晶アダクトＤ−１は、第１再溶解工程Ｃ−１に導入さ
れ、次段の第２固液分離工程Ｂ−２からの第２結晶アダ
クト洗浄排液Ｅ−２によって溶解された後、ライン３を
通って第２晶析工程Ａ−２に導入される。The crystallization product obtained in the first crystallization step A-1 is introduced into the first solid-liquid separation step B-1 through the line 2, where the first crystal adduct D-1 and the first crystal adduct D-1 are introduced. 1 mother liquor F-1 and the first mother liquor F-1 contains phenol,
Since it contains useful components such as bisphenol A, after suitable treatment, it is recycled to the reaction step between phenol and acetone. The first crystal adduct separated from the first crystallization product was washed with the second mother liquor F-2 obtained in the next second solid-liquid separation step B-2, and the first crystal obtained in this washing was used. The cleaning effluent E-1 is circulated to the reaction step of phenol and acetone. As described above, the first was washed with the second mother liquor F-2.
The crystal adduct D-1 was introduced into the first re-dissolution step C-1, and was dissolved by the second crystal adduct cleaning waste liquid E-2 from the second solid-liquid separation step B-2 at the next stage, and then the line It is introduced into the second crystallization step A-2 through No. 3.
【０００７】第２晶析工程Ａ−２で得られた晶析生成物
はライン４を通って第２固液分離工程Ｂ−２に導入さ
れ、ここで第２結晶アダクトＤ−２と第２母液Ｆ−２と
に分離され、第２母液Ｆ−２は、前記のように第１固液
分離工程Ｂ−１で分離された結晶アダクトＤ−１を洗浄
するのに使用される。一方、第２結晶アダクトＤ−２
は、次段の第３固液分離工程Ｂ−３で得られた第３母液
Ｆ−３で洗浄され、その第２洗浄排液Ｅ−２は、前記の
ように、第１再溶解工程Ｃ−１における第１結晶アダク
トＤ−１の溶解用のフェノ−ル溶液として用いられる。
前記のように、第３母液Ｆ−３で洗浄された第２結晶ア
ダクトＤ−２は、第２再溶解工程Ｃ−２に導入され、次
段の第３固液分離工程Ｂ−３からの第３結晶アダクト洗
浄排液Ｅ−３によって溶解された後、ライン５を通って
第３晶析工程Ａ−３に導入される。The crystallization product obtained in the second crystallization step A-2 is introduced into the second solid-liquid separation step B-2 through the line 4, where the second crystal adduct D-2 and the second crystal adduct D-2 are introduced. The second mother liquor F-2, which is separated into the mother liquor F-2, is used to wash the crystal adduct D-1 separated in the first solid-liquid separation step B-1 as described above. On the other hand, the second crystal adduct D-2
Is washed with the third mother liquor F-3 obtained in the subsequent third solid-liquid separation step B-3, and the second washing effluent E-2 is, as described above, the first re-dissolution step C. -1 used as a phenol solution for dissolving the first crystal adduct D-1.
As described above, the second crystal adduct D-2 washed with the third mother liquor F-3 is introduced into the second re-dissolution step C-2, and the second solid adduct D-3 is separated from the third solid-liquid separation step B-3 in the next stage. After being dissolved by the third crystal adduct cleaning effluent E-3, it is introduced into the third crystallization step A-3 through the line 5.
【０００８】第３晶析工程Ａ−３で得られた晶析生成物
はライン６を通って第３固液分離工程Ｂ−３に導入さ
れ、ここで第３結晶アダクトＤ−３と第３母液Ｆ−３と
に分離され、第３母液Ｆ−３は、前記のように第２固液
分離工程Ｂ−２で分離された第２結晶アダクトＤ−２を
洗浄するのに使用される。第３結晶アダクトＤ−３は、
精製フェノ−ルＦによって洗浄され、その第３洗浄排液
Ｅ−３は、前記のように、第２再溶解工程Ｃ−２におけ
る第２結晶アダクトＤ−２の溶解用フェノ−ル溶液とし
て用いられる。第３固液分離工程で得られる精製フェノ
−ルＦで洗浄された第３結晶アダクトＤ−３は、製品と
して回収される。The crystallization product obtained in the third crystallization step A-3 is introduced into the third solid-liquid separation step B-3 through the line 6, where the third crystal adduct D-3 and the third crystal adduct D-3 are added. Separated into mother liquor F-3, the third mother liquor F-3 is used to wash the second crystal adduct D-2 separated in the second solid-liquid separation step B-2 as described above. The third crystal adduct D-3 is
It was washed with the purified phenol F, and the third washing waste liquid E-3 was used as a phenol solution for dissolving the second crystal adduct D-2 in the second re-dissolving step C-2 as described above. Be done. The third crystal adduct D-3 washed with the purified phenol F obtained in the third solid-liquid separation step is recovered as a product.
【０００９】本発明において、精製フェノ−ルＦとして
は、通常、その溶融色ＡＰＨＡが好ましくは１５以下の
ものであれば任意のものが用いられる。本発明で好まし
く用いることのできる精製フェノ−ルとしては、例え
ば、（ｉ）フェノ−ルとアセトンとの反応生成物から分
離されたフェノ−ル、（ｉｉ）ビスフェノ−ルを含むフ
ェノ−ルの晶析生成物から分離されたフェノ−ル、（ｉ
ｉｉ）結晶アダクトを洗浄した後の使用済みフェノ−ル
及び工業用フェノ−ルの中から選ばれる少なくとも一種
のフェノ−ルの精製物が用いられる。フェノ−ルとアセ
トンとの反応により得られる反応生成物は、それに含ま
れる生成ビスフェノ−ルＡを濃縮するために、その反応
生成物からフェノ−ルが分離されるが、本発明では、こ
のフェノ−ルの精製物を洗浄液として用いることができ
る。また、ビスフェノ−ルＡを含むフェノ−ルを晶析処
理して結晶アダクトを析出させる場合、通常、複数段の
晶析工程と晶析生成物の固液分離工程が採用され、それ
に応じて複数種の母液（フェノ−ル溶液）が得られる
が、本発明ではこれらの母液を形成するフェノ−ルの精
製物を洗浄液として用いることができる。本発明で用い
るフェノールの精製物は、それら母液のいずれの母液を
形成するフェノールの精製物でも良いが、好ましくは最
終段の晶析工程で得られる晶析生成物から分離されたフ
ェノールの精製物を用いるのがよい。本発明において
は、結晶アダクトを洗浄した後には使用済みのフェノ−
ルが得られるが、本発明では、この使用済のフェノ−ル
の精製物も洗浄液として有利に用いることができる。本
発明で用いる前記フェノ−ル精製物を得るための原料フ
ェノ−ルとしては、その純度が９９重量％以上、好まし
くは９９．５％重量％以上のものの使用が好ましい。ま
た、本発明では、工業用フェノ−ルの精製物を洗浄液と
して用いることができる。この場合、工業用フェノ−ル
としては、好ましくはフェノ−ル純度９９．５重量％以
上のものが用いられる。In the present invention, as the purified phenol F, any one can be used as long as its melt color APHA is preferably 15 or less. Examples of the purified phenol that can be preferably used in the present invention include phenol separated from the reaction product of (i) phenol and acetone, and (ii) phenol containing bisphenol. A phenol separated from the crystallized product, (i
ii) A purified product of at least one phenol selected from spent phenol after washing the crystal adduct and industrial phenol is used. The reaction product obtained by the reaction of phenol and acetone is separated from the reaction product in order to concentrate the produced bisphenol A contained therein. In the present invention, this phenol is separated. Can be used as a washing liquid. Further, in the case of crystallizing a phenol containing bisphenol A to precipitate a crystal adduct, a plurality of stages of crystallization and a solid-liquid separation step of a crystallization product are usually adopted, and a plurality of crystallization steps are accordingly performed. A seed mother liquor (phenol solution) is obtained, but in the present invention, a purified product of phenol forming these mother liquors can be used as a washing liquid. The purified product of phenol used in the present invention may be a purified product of phenol forming any of the mother liquors, but is preferably a purified product of phenol separated from the crystallization product obtained in the final crystallization step. It is better to use. In the present invention, after cleaning the crystal adduct, used pheno-
However, in the present invention, the purified product of the used phenol can be advantageously used as a washing liquid. As the raw material phenol for obtaining the purified phenol product used in the present invention, it is preferable to use one having a purity of 99% by weight or more, preferably 99.5% by weight or more. Further, in the present invention, a purified product of industrial phenol can be used as a cleaning liquid. In this case, as the industrial phenol, one having a phenol purity of 99.5% by weight or more is preferably used.
【００１０】前記フェノ−ルの精製を好ましく行う場
合、その原料フェノ−ルは、先ず、強酸型イオン交換樹
脂と接触させて処理するが、この場合、強酸型イオン交
換樹脂としては、スルホン基を有するものが用いられ、
このような強酸型イオン交換樹脂は、従来良く知られて
いるものである。例えば、ロ−ムアンドハ−ス社から入
手し得るアンバ−ライト及びアンバ−リストや、三菱化
成社から入手し得るダイヤイオン等を好ましく用いるこ
とができる。この強酸型イオン交換樹脂を用いるフェノ
−ルの処理は、強酸型イオン交換樹脂を含む充填塔にフ
ェノ−ルを流通させる方法や、強酸型イオン交換樹脂を
入れた撹拌槽にフェノ−ルを入れて撹拌する方法等によ
り実施することができる。処理温度は４５〜１５０℃、
好ましくは５０〜１００℃である。強酸型イオン交換樹
脂とフェノ−ルの接触時間は、５〜２００分、好ましく
は１５〜６０分程度である。この強酸型イオン交換樹脂
を用いてフェノ−ルの処理を行う場合、フェノ−ル中の
水分は、０．５重量％以下、好ましくは０．１重量％以
下にする。これより水分が多くなると、強酸型イオン交
換樹脂による不純物除去効果が悪化する。フェノ−ル中
からの０．５重量％以下までの水分の除去は、フェノ−
ル中に公知の共沸剤を加え共沸させることによって行う
ことができる。前記強酸型イオン交換樹脂と接触処理さ
れたフェノ−ルは、高沸点不純物を含むもので、蒸留処
理することにより、その高沸点不純物を蒸留残渣として
分離する。When the above-mentioned phenol is preferably purified, the starting phenol is treated by contacting it with a strong acid type ion exchange resin. In this case, the strong acid type ion exchange resin has a sulfone group. What you have is used,
Such a strong acid type ion exchange resin is well known in the prior art. For example, Amberlite and Amberlist available from Rohm and Haas, or Diaion available from Mitsubishi Kasei can be preferably used. The treatment of the phenol with the strong acid type ion exchange resin is carried out by flowing the phenol through a packed column containing the strong acid type ion exchange resin, or by putting the phenol in a stirring tank containing the strong acid type ion exchange resin. It can be carried out by a method such as stirring. The processing temperature is 45 to 150 ° C,
It is preferably 50 to 100 ° C. The contact time between the strong acid type ion exchange resin and the phenol is 5 to 200 minutes, preferably about 15 to 60 minutes. When the phenol is treated using this strong acid ion exchange resin, the water content in the phenol is 0.5% by weight or less, preferably 0.1% by weight or less. If the water content is larger than this, the effect of removing impurities by the strong acid ion exchange resin deteriorates. Removal of water up to 0.5% by weight from the phenol is
It can be carried out by adding a known azeotropic agent to the resin and azeotropically boiling it. The phenol that has been contact-treated with the strong acid ion exchange resin contains high-boiling impurities, and is subjected to a distillation treatment to separate the high-boiling impurities as a distillation residue.
【００１１】蒸留塔の運転条件はフェノ−ルと高沸点不
純物が分離できればよいが、留出フェノ−ル中に高沸点
不純物が混入しない条件で行う必要があり、留意すべき
ポイントとして蒸留処理温度を２００℃以下にすること
である。２００℃以下の温度であれば運転圧力は任意に
設定されるが、通常５０Ｔｏｒｒ〜６００Ｔｏｒｒの減
圧下で行われる。運転温度が２００℃をこえると高沸点
不純物等の分解がおこり精製フェノ−ルの品質を低下さ
せるので好ましくない。前記処理によって得られた精製
フェノ−ルは、ＡＰＨＡ基準の色相が１０以下のもので
あり、製品結晶アダクトに付着しても、その色相を特に
悪化させることはない。The operating conditions of the distillation column should be such that the phenol and the high-boiling impurities can be separated, but it is necessary to carry out the conditions under which the high-boiling impurities are not mixed in the distillate phenol. Is to be 200 ° C. or less. The operating pressure is arbitrarily set at a temperature of 200 ° C. or lower, but is usually performed under a reduced pressure of 50 Torr to 600 Torr. When the operating temperature exceeds 200 ° C., high-boiling impurities and the like are decomposed and the quality of the purified phenol is deteriorated, which is not preferable. The purified phenol obtained by the above treatment has an APHA standard hue of 10 or less, and even if it adheres to the product crystal adduct, the hue is not particularly deteriorated.
【００１２】本発明においては、各段の結晶アダクトの
洗浄液としては、その少なくとも一部に次段からの母液
を用いるが、この場合、必要に応じ、次段からの洗浄液
の一部を併用することも可能である。また、各段の再溶
解工程における結晶アダクト溶解用のフェノ−ル溶液と
しては、その少なくとも一部に、次段からの洗浄排液を
用いるが、この場合、必要に応じ、次段からの母液の一
部を併用することができる。本発明において結晶アダク
トの洗浄に用いる洗浄液及び結晶アダクトを溶解させる
ためのフェノ−ル溶液は、いずれも、それに含まれる不
純物濃度が、下流側、即ち、第１段の晶析工程から第ｎ
段の晶析工程に向うにつれて、小さくなっている。換言
すれば、各段において用いられる結晶アダクト洗浄液及
び結晶アダウト溶解用フェノ−ル溶液中の不純物濃度
は、次段におけるそれよりも、大きくなっている。隣接
する各段で用いられる洗浄液中の不純物濃度は、ほぼ等
比級数的に減少する。なお、本明細書で言う不純物と
は、フェノールとアセトンとの反応でビスフェノールＡ
を生成する際の副生成物を意味するものである。このよ
うな不純物には、ビスフェノールＡの異性体、クロマン
化合物等が包含される。更に、本発明では、製品アダク
トの要求純度に応じて、第１段目から第ｎ−１段目まで
の各洗浄工程の一部を省略し、固液分離工程で得られた
結晶アダクトを、そのまま次段の再溶解工程へもってく
ることもできる。この場合、再溶解工程に用いるフェノ
ール溶液は、次段の固液分離工程で得られた母液（又は
洗浄排液）を用いる。このように、本発明では、製品ア
ダクトの要求純度に応じて、各段にて使用される洗浄用
フェノール溶液の量を調整することにより、全体として
のフェノールの使用量を下げ、コストを抑えることも可
能である。本発明における晶析工程は、２段以上であ
り、図面においては３段の晶析工程を含む例を示した
が、４段以上の晶析工程であっても、前記と同様にして
実施することができる。In the present invention, the mother liquor from the next stage is used as at least a part of the cleaning liquid for the crystal adduct in each stage. In this case, a part of the cleaning liquid from the next stage is used in combination, if necessary. It is also possible. Further, as the phenol solution for dissolving the crystal adduct in the redissolution step of each stage, at least a part of it is used as the cleaning drainage from the next stage, but in this case, if necessary, the mother liquor from the next stage is used. Can be used in combination. In the present invention, both the cleaning solution used for cleaning the crystal adduct and the phenol solution for dissolving the crystal adduct have an impurity concentration contained in the cleaning solution on the downstream side, that is, from the first crystallization step to the n-th step.
It becomes smaller as it goes to the stage crystallization process. In other words, the impurity concentration in the crystal adduct cleaning solution and the crystal adout dissolving phenol solution used in each stage is higher than that in the next stage. The impurity concentration in the cleaning liquid used in each adjacent stage decreases almost in a geometrical series. The term "impurity" used herein means bisphenol A by the reaction of phenol and acetone.
Means a by-product in the production of. Such impurities include isomers of bisphenol A, chroman compounds, and the like. Furthermore, in the present invention, depending on the required purity of the product adduct, a part of each washing step from the first step to the n-1th step is omitted, and the crystal adduct obtained in the solid-liquid separation step is It is also possible to directly proceed to the next redissolution step. In this case, as the phenol solution used in the redissolving step, the mother liquor (or the washing effluent) obtained in the subsequent solid-liquid separation step is used. As described above, in the present invention, the amount of the phenol solution for cleaning used in each stage is adjusted according to the required purity of the product adduct, thereby reducing the amount of phenol used as a whole and suppressing the cost. Is also possible. The crystallization process in the present invention has two or more stages, and the drawings show an example including three stages of crystallization processes, but four or more stages of crystallization processes are carried out in the same manner as above. be able to.
【００１３】[0013]
【発明の効果】本発明によれば、最終段の結晶アダクト
の洗浄のみに精製フェノ−ルを用いるだけで、高品位の
結晶アダクトを得ることができる。従って、本発明では
高純度精製フェノ−ルノ使用量が少なくてすみ、結晶ア
ダクトの製造コストが低くてすむという利点がある。According to the present invention, a high-quality crystal adduct can be obtained by using purified phenol only for cleaning the final stage crystal adduct. Therefore, according to the present invention, there is an advantage that the amount of high-purity purified phenol used is small and the production cost of the crystal adduct is low.
【００１４】[0014]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００１５】参考例１ アセトン及びフェノ−ルを、酸触媒存在下で反応させて
得た反応生成物を濃縮し、５０℃で晶析して、ビスフェ
ノ−ルＡ・フェノ−ルアダクト２０ｗｔ％の晶析スラリ
−３０００ｇを得た。これを５０℃で減圧濾過（このと
き得られた濾過後の母液（２２５０ｇ）をＡとする）し
て得られた結晶アダクトを別途用意した精製フェノ−ル
６００ｇを用いて洗浄濾過した（このとき得られた洗浄
排液５８０ｇをＢとする）。洗浄後の結晶アダクトを別
途用意した精製フェノ−ル（ＡＰＨＡ：５）１３１０ｇ
に再溶解し、５０℃において晶析し、ビスフェノ−ルＡ
・フェノ−ルアダクト２０ｗｔ％のスラリ−を得、これ
を５０℃で減圧濾過（このとき得られた母液１４３０ｇ
をＣとする）した後、別途用意した精製フェノ−ル６０
０ｇにて、２回洗浄濾過を行った（このとき得られた１
回目の洗浄排液５８０ｇをＤ、２回目の洗浄排液５８０
ｇをＥとする）。こうして得られたビスフェノ−ル・フ
ェノ−ル結晶アダクトの不純物濃度は１００ｗｔｐｐ
ｍ、溶融色は５ＡＰＨＡであった。Reference Example 1 Acetone and phenol were reacted in the presence of an acid catalyst to concentrate the reaction product, which was then crystallized at 50 ° C. to give 20 wt% bisphenol A / phenol adduct crystals. Deposition slurry-3000 g was obtained. This was filtered under reduced pressure at 50 ° C. (the mother liquor after filtration (2250 g) obtained at this time was designated as A) and the obtained crystal adduct was washed and filtered using 600 g of separately prepared purified phenol (at this time). 580 g of the obtained cleaning drainage liquid is designated as B). 1310 g of purified phenol (APHA: 5), which was prepared separately from the washed crystal adduct.
Redissolved in bisphenol A and crystallized at 50 ° C.
A phenol adduct 20 wt% slurry was obtained, which was filtered under reduced pressure at 50 ° C. (1430 g of the mother liquor obtained at this time).
To C), and then separately prepared purified phenol 60
Washing filtration was performed twice at 0 g (1 obtained at this time).
580 g of second washing drainage 580 D of second washing drainage
Let g be E). The impurity concentration of the bisphenol-phenol crystal adduct thus obtained was 100 wtpp.
m, and the melt color was 5 APHA.
【００１６】実施例１ 参考例１と同じく、アセトン及びフェノ−ルを酸触媒存
在下にて反応させて得た反応生成物を濃縮し、５０℃の
温度で晶析して、ビスフェノ−ルＡ，フェノ−ル結晶ア
ダクト２０ｗｔ％の晶析スラリ−３０００ｇを得た。こ
れを５０℃で減圧濾過して得られた結晶アダクトを参考
例１の母液Ｃ７００ｇにて洗浄した。洗浄後の結晶アダ
クトを参考例１の母液Ｃの残り７３０ｇと、洗浄排液Ｄ
５８０ｇを加えて再溶解したのち、５０℃にて晶析し、
ビスフェノ−ルＡ・フェノ−ル結晶アダクト２０ｗｔ％
の晶析スラリ−を得、これを５０℃で減圧濾過した。次
いで、得られた結晶アダクトを、参考例１の洗浄排液Ｅ
５８０ｇで洗浄した後、更に最終洗浄工程として精製フ
ェノ−ル６００ｇにて洗浄した。このとき得られたビス
フェノ−ルＡ・フェノ−ル結晶アダクトの不純物濃度は
参考例と同じ１００ｗｔｐｐｍであり、かつ溶融色も５
ＡＰＨＡを示した。従がって、本実施例においては、最
終段の洗浄高手に精製フェノ−ルを用いただけで、残り
はすべて、工程の後段側から回収された母液ないし洗浄
液を使用したことになり、精製フェノ−ルの使用量を少
なくし、高品位のビスフェノ−ルＡ・フェノ−ル結晶ア
ダクト、ひいては、高品位ビスフェノ−ルＡを得ること
がせきる。Example 1 As in Reference Example 1, the reaction product obtained by reacting acetone and phenol in the presence of an acid catalyst was concentrated and crystallized at a temperature of 50 ° C. to give bisphenol A. , 3,000 g of a crystallization slurry having a phenol crystal adduct of 20 wt% was obtained. The crystal adduct obtained by filtration under reduced pressure at 50 ° C. was washed with 700 g of mother liquor C of Reference Example 1. The crystal adduct after washing was treated with the remaining 730 g of mother liquor C of Reference Example 1 and washing effluent D.
580 g was added and redissolved, followed by crystallization at 50 ° C.,
Bisphenol A / phenol crystal adduct 20 wt%
The crystallization slurry of was obtained, which was filtered under reduced pressure at 50 ° C. Then, the obtained crystal adduct was washed with the cleaning drainage E of Reference Example 1.
After washing with 580 g, 600 g of purified phenol was used as the final washing step. The impurity concentration of the bisphenol A / phenol crystal adduct obtained at this time was 100 wtppm, which was the same as in the reference example, and the melt color was 5
APHA is shown. Therefore, in this example, only the purified phenol was used for the final stage of washing, and the rest of the product used the mother liquor or the washing liquid recovered from the latter stage of the process. It is possible to obtain a high-quality bisphenol A / phenol crystal adduct, and by extension, a high-quality bisphenol A, by reducing the amount of the bisphenol used.
【図１】本発明の方法を実施する場合のフロ−シ−トの
１例を示す。FIG. 1 shows an example of a flow sheet for carrying out the method of the present invention.
Ａ−１、Ａ−２、Ａ−３ 晶析工程 Ｂ−１、Ｂ−２、Ｂ−３ 固液分離工程 Ｃ−１、Ｃ−２ 再溶解工程 A-1, A-2, A-3 Crystallization step B-1, B-2, B-3 Solid-liquid separation step C-1, C-2 Redissolution step
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安井 誠 神奈川県横浜市鶴見区鶴見中央二丁目12番 １号 千代田化工建設株式会社内 (72)発明者 浅岡 佐知夫 神奈川県横浜市鶴見区鶴見中央二丁目12番 １号 千代田化工建設株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Makoto Yasui Makoto Yasui, 2-12-1, Tsurumi Chuo, Tsurumi-ku, Yokohama-shi, Kanagawa Chiyoda Kako Construction Co., Ltd. Chome 12-1 Chiyoda Kako Construction Co., Ltd.
Claims (1)
を、ｎ（ｎ≧２）段の晶析工程、ｎ段の固液分離工程、
少なくとも１段のビスフェノ−ルＡ・フェノ−ル結晶ア
ダクト洗浄工程及びｎ−１段の結晶アダクト再溶解工程
を含み、第１段目から第ｎ−１段目の各段の晶析工程で
得られた晶析生成物を固液分離し、得られた結晶アダク
トをそのままあるいは洗浄液で洗浄した後、フェノ−ル
溶液で再溶解して次段の晶析工程に供給し、かつ第ｎ段
目の晶析工程で得られた晶析生成物を固液分離し、得ら
れた結晶アダクトを洗浄液で洗浄して高純度の結晶アダ
クトを得る方法において、（ａ）第ｎ段目の固液分離工
程で得られた第ｎ番目の結晶アダクトの洗浄液の少なく
とも一部に、精製フェノ−ルを用いること、（ｂ）少な
くとも第ｎ−１段目の固液分離工程で得られた結晶アダ
クトの再溶解用フェノ−ル溶液の少なくとも一部に、第
ｎ段目の固液分離工程で得られた結晶アダクトの洗浄排
液又は第ｎ段目の固液分離工程で得られた母液を用いる
こと、（ｃ）少なくとも第ｎ−１段目の固液分離工程で
得られた結晶アダクトの洗浄液の少なくとも一部に、第
ｎ段目の固液分離工程で得られた母液又は第ｎ段目の固
液分離工程で得られた結晶アダクトの洗浄排液を用いる
こと、（ｄ）第１段目から第ｎ−１段目までの各段にお
ける結晶アダクト再溶解用フェノ−ル溶液中の不純物濃
度及び結晶アダクト洗浄液中の不純物濃度が、いずれも
次段における結晶アダクト再溶解用フェノ−ル溶液中の
不純物濃度及び結晶アダクト洗浄液中の不純物濃度より
も高いこと、を特徴とするヒズフェノ−ルＡ・フェノ−
ル結晶アダクトの製造方法。1. A phenol solution containing bisphenol A is subjected to n (n ≧ 2) stage crystallization step, n stage solid-liquid separation step,
It includes at least one stage of bisphenol A / phenol crystal adduct washing step and n-1 stage of crystal adduct redissolving step, and is obtained by the crystallization step of each stage from the 1st stage to the n-1th stage. The obtained crystallization product is subjected to solid-liquid separation, and the obtained crystal adduct is washed as it is or with a washing solution, and then redissolved in a phenol solution and supplied to the crystallization step of the next stage, and the n-th stage. In the method for solid-liquid separation of the crystallization product obtained in the crystallization step, and washing the obtained crystal adduct with a washing liquid to obtain a high-purity crystal adduct, (a) solid-liquid separation of the nth stage The purified phenol is used as at least a part of the washing liquid of the n-th crystal adduct obtained in the step, and (b) the recrystallization of the crystal adduct obtained in at least the (n-1) th solid-liquid separation step. At least a part of the phenol solution for dissolution is used for solid-liquid separation in the nth stage. Using the cleaning effluent of the crystal adduct obtained in the above step or the mother liquor obtained in the n-th solid-liquid separation step, (c) the crystal obtained in at least the (n-1) -th solid-liquid separation step Use of the mother liquor obtained in the n-th solid-liquid separation step or the crystal adduct washing effluent obtained in the n-th solid-liquid separation step as at least a part of the adduct cleaning solution, (d) The impurity concentration in the crystal adduct re-dissolving phenol solution and the impurity concentration in the crystal adduct cleaning solution in each stage from the first stage to the (n-1) -th stage are both in the next stage. -Hisphenol A. phenol, which is higher than the impurity concentration in the solution and the crystal adduct cleaning solution.
Le crystal adduct manufacturing method.
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30652491A JP2796556B2 (en) | 1991-10-25 | 1991-10-25 | Method for producing high-grade bisphenol A / phenol crystal adduct |
| ES96200436T ES2126977T3 (en) | 1991-07-10 | 1992-05-29 | PROCEDURE FOR THE PRODUCTION OF CRYSTALLINE ADDICT OF BISPHENOL A AND PHENOL. |
| EP92304932A EP0522700B1 (en) | 1991-07-10 | 1992-05-29 | Process for the production of crystalline adduct of bisphenol A and phenol and apparatus therefor |
| EP96200435A EP0718267B1 (en) | 1991-07-10 | 1992-05-29 | Process for the production of crystalline adduct of bisphenol A and phenol and apparatus therefor |
| DE69227850T DE69227850T2 (en) | 1991-07-10 | 1992-05-29 | Process for the preparation of a crystalline adduct of bisphenol A with phenol |
| DE69227849T DE69227849T2 (en) | 1991-07-10 | 1992-05-29 | Process and preparation of a crystalline adduct of bisphenol A with phenol and device therefor |
| DE69217133T DE69217133T2 (en) | 1991-07-10 | 1992-05-29 | Process for the preparation of a crystalline adduct of bisphenol A with phenol and device therefor |
| ES96200435T ES2126976T3 (en) | 1991-07-10 | 1992-05-29 | PROCEDURE FOR THE PRODUCTION OF CRYSTALLINE ADDICT OF BISPHENOL A AND PHENOL AND APPARATUS FOR THIS. |
| EP96200436A EP0718268B1 (en) | 1991-07-10 | 1992-05-29 | Process for the production of crystalline adduct of bisphenol A and phenol |
| ES92304932T ES2097877T3 (en) | 1991-07-10 | 1992-05-29 | PROCEDURE FOR THE PREPARATION OF A CRYSTALLINE ADDICT OF BISPHENOL A WITH PHENOL AND APPARATUS FOR IT. |
| CNB991038622A CN1190404C (en) | 1991-07-10 | 1992-06-30 | Condensation treatment method of desorbed gas containing phenolic compound, bisphenol A and steam |
| CNB991038959A CN1167659C (en) | 1991-07-10 | 1992-06-30 | Phenol refining, bisphenol A·phenol crystal adduct refining and production method, bisphenol A production method |
| CNB991038614A CN1190403C (en) | 1991-07-10 | 1992-06-30 | Crystallization device, preparation method and device of bisphenol A·phenol crystal adduct |
| KR1019920012309A KR100189205B1 (en) | 1991-07-10 | 1992-07-10 | Process for the production of crystalline adduct of bisphenol and phenol and apparatus therefor |
| US08/026,126 US5345000A (en) | 1991-07-10 | 1993-03-03 | Process for the production of crystalline adduct of bisphenol A and phenol and apparatus therefor |
| KR1019980044544A KR100190334B1 (en) | 1991-07-10 | 1998-10-23 | Purification method of phenol, bisphenol A. Method for Purifying Phenolic Crystal Additives, Method for Preparing This Crystal Additive, Crystalline Apparatus and Method for Preparing Bisphenol A |
| KR1019980044545A KR100190335B1 (en) | 1991-07-10 | 1998-10-23 | Method of purifying bisphenol a. phenol crystalline adduct, method of producing the crystalline adduct, and method of producing bisphenol a. |
| KR1019980044546A KR100190336B1 (en) | 1991-07-10 | 1998-10-23 | Method of purifying bisphenol a, phenol crystalline adduct, method of producing the crystalline adduct, and method of producing bisphenol a. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30652491A JP2796556B2 (en) | 1991-10-25 | 1991-10-25 | Method for producing high-grade bisphenol A / phenol crystal adduct |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05117194A true JPH05117194A (en) | 1993-05-14 |
| JP2796556B2 JP2796556B2 (en) | 1998-09-10 |
Family
ID=17958068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30652491A Expired - Lifetime JP2796556B2 (en) | 1991-07-10 | 1991-10-25 | Method for producing high-grade bisphenol A / phenol crystal adduct |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796556B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053512A (en) * | 1999-12-03 | 2002-02-19 | Mitsui Chemicals Inc | High-quality bisphenol a and method for producing the same |
| JP2005232134A (en) * | 2004-02-23 | 2005-09-02 | Mitsubishi Chemicals Corp | Method for producing bisphenol A |
-
1991
- 1991-10-25 JP JP30652491A patent/JP2796556B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053512A (en) * | 1999-12-03 | 2002-02-19 | Mitsui Chemicals Inc | High-quality bisphenol a and method for producing the same |
| JP2005232134A (en) * | 2004-02-23 | 2005-09-02 | Mitsubishi Chemicals Corp | Method for producing bisphenol A |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2796556B2 (en) | 1998-09-10 |
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