JPH0625042A - Production of 2,2-bis@(3754/24)4-hydroxyphenyl)propane - Google Patents
Production of 2,2-bis@(3754/24)4-hydroxyphenyl)propaneInfo
- Publication number
- JPH0625042A JPH0625042A JP4180892A JP18089292A JPH0625042A JP H0625042 A JPH0625042 A JP H0625042A JP 4180892 A JP4180892 A JP 4180892A JP 18089292 A JP18089292 A JP 18089292A JP H0625042 A JPH0625042 A JP H0625042A
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- exchange resin
- catalyst
- bisphenol
- reactor
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title 1
- 239000001294 propane Substances 0.000 title 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 73
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 230000006866 deterioration Effects 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims 1
- 229920003303 ion-exchange polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005341 cation exchange Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 alkyl mercaptans Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、２，２−ビス（４−ヒ
ドロキシフェニル）プロパン（以下、ビスフェノールＡ
と略す。）の製造方法の改良に関するものである。さら
に、詳しくは触媒として陽イオン交換樹脂を用いて、連
続的にビスフェノールＡを製造するに際して、ビスフェ
ノールＡの収率向上と該陽イオン交換樹脂の寿命延長を
もたらすビスフェノールＡの製造方法に関するものであ
る。The present invention relates to 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A).
Abbreviated. ) Related to the improvement of the manufacturing method. More specifically, the present invention relates to a method for producing bisphenol A which improves the yield of bisphenol A and extends the life of the cation exchange resin when continuously producing bisphenol A using a cation exchange resin as a catalyst. .
【０００２】[0002]
【従来の技術】ビスフェノールＡ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は、
酸性触媒及び場合により用いられる硫黄化合物などの助
触媒の存在下に、過剰のフェノールとアセトンとを縮合
させることにより製造される。そして、該酸性触媒とし
ては、最近陽イオン交換樹脂が注目され、この陽イオン
交換樹脂を用いてビスフェノールＡを製造する方法が実
用化されている。この場合、通常、該陽イオン交換樹脂
を充填した反応器を直列に配置した多段反応器に、フェ
ノールとアセトンと、場合により用いられる助触媒とを
含む原料混合物を連続的に供給して反応させ、ビスフェ
ノールＡを生成させる方法が採られている。このような
反応様式においては、通常、前段の反応器ほど触媒の劣
化が大きくなる。そこで、より劣化した触媒を新しい触
媒と交換する場合、新しい触媒と交換する場所、すなわ
ち最前段にもってくると、触媒が有効に利用されず、反
応器トータルでのビスフェノールＡの収率が低下し、か
つ触媒の劣化も速くなるという好ましくない事態を招来
する。また、陽イオン交換樹脂触媒を用いてビスフェノ
ールＡを製造する方法において、劣化した触媒を交換す
る方法については、これまでなんら報告がなされていな
い。2. Description of the Related Art Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin, or epoxy resin, and the demand for it is increasing in recent years. . This bisphenol A is
It is prepared by condensing excess phenol with acetone in the presence of an acidic catalyst and optionally a cocatalyst such as a sulfur compound. As the acidic catalyst, a cation exchange resin has recently attracted attention, and a method for producing bisphenol A using this cation exchange resin has been put into practical use. In this case, usually, a raw material mixture containing phenol, acetone, and optionally a cocatalyst is continuously supplied to a multistage reactor in which the reactors filled with the cation exchange resin are arranged for reaction. , Bisphenol A is produced. In such a reaction mode, the deterioration of the catalyst is usually greater in the reactor in the first stage. Therefore, when replacing a more deteriorated catalyst with a new catalyst, if the catalyst is brought to the place where it is replaced with a new catalyst, that is, at the frontmost stage, the catalyst is not used effectively and the yield of bisphenol A in the total reactor decreases. In addition, the deterioration of the catalyst is accelerated, which is an undesirable situation. Further, in the method for producing bisphenol A using a cation exchange resin catalyst, no report has been made so far on a method for replacing a deteriorated catalyst.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、触媒として陽イオン交換樹脂触媒を用い
て、連続的にビスフェノールＡを製造するに際して、ビ
スフェノールＡの収率を向上させるとともに、該陽イオ
ン交換樹脂の寿命を延長させるビスフェノールＡの製造
方法を提供することを目的としてなされたものである。Under these circumstances, the present invention improves the yield of bisphenol A when continuously producing bisphenol A using a cation exchange resin catalyst as a catalyst. The purpose of the present invention is to provide a method for producing bisphenol A which extends the life of the cation exchange resin.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた。その結果、陽イオ
ン交換樹脂を充填した少なくとも２基の反応器が直列に
配置された多段反応器を用いてビスフェノールＡを連続
的に製造する方法において、触媒の劣化がより進行した
陽イオン交換樹脂を新たな又は再生した陽イオン交換樹
脂と交換する場合、該新たに又は再生した陽イオン交換
樹脂を充填した反応器を、反応系の後段に設置すること
により、その目的を達成し得ることを見出した。本発明
は、このような知見に基づいて完成したものである。す
なわち、本発明は、触媒として陽イオン交換樹脂を充填
した少なくとも２基の反応器が直列に配置された多段反
応器に、フェノールとアセトンとを含む原料混合物を連
続的に供給してビスフェノールＡを製造する方法におい
て、触媒劣化のより進行した陽イオン交換樹脂に代え
て、新たな又は再生した陽イオン交換樹脂を反応に供す
るに当たり、該新たな又は再生した陽イオン交換樹脂を
充填した反応器を反応系の後段に設置することを特徴と
するビスフェノールＡの製造方法を提供するものであ
る。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object. As a result, in a method for continuously producing bisphenol A using a multi-stage reactor in which at least two reactors filled with a cation exchange resin are arranged in series, a cation exchange resin in which catalyst deterioration is more advanced In the case of exchanging the cation exchange resin with a new or regenerated cation exchange resin, it is possible to achieve the purpose by installing a reactor filled with the newly or regenerated cation exchange resin in the latter stage of the reaction system. I found it. The present invention has been completed based on such findings. That is, according to the present invention, a raw material mixture containing phenol and acetone is continuously supplied to a multi-stage reactor in which at least two reactors filled with a cation exchange resin as a catalyst are arranged in series to obtain bisphenol A. In the production method, a new or regenerated cation exchange resin is used in the reaction in place of the cation exchange resin with more advanced catalyst deterioration, and a reactor filled with the new or regenerated cation exchange resin is used. The present invention provides a method for producing bisphenol A, which is characterized in that it is installed in the latter stage of the reaction system.
【０００５】本発明においては、触媒として陽イオン交
換樹脂を充填した少なくとも２基の反応器が直列に配置
された多段反応器に、フェノールとアセトンとを含む原
料混合物を連続的に供給して反応させるのに、固定床多
段連続反応方式が用いられる。該原料混合物には、フェ
ノール及びアセトン以外に、所望により選択率や反応速
度を上げる目的で助触媒を加えてもよい。この助触媒と
しては、例えば、メチルメルカプタン，エチルメルカプ
タン，ｎ−オクチルメルカプタンなどのアルキルメルカ
プタン類、チオグリコール酸，β−メルカプトプロピオ
ン酸などのチオカルボン酸類、２−アミノエタンチオー
ルなどのアミノアルカンチオール類、メルカプトエタノ
ールなどのメルカプトアルコール類などが挙げられる。
また、アセトン／フエノールモル比は、通常１／３０〜
１／３、好ましくは１／１５〜１／５の範囲で選ばれ
る。このモル比が１／３０未満では、反応速度が遅すぎ
るし、また、１／３を超えると、不純物の生成が多くな
り、ビスフェノールＡの選択率が低下する。一方、該助
触媒／アセトンモル比は、通常、0.１／１００〜２０／
１００、好ましくは１／１０〜１０／１００の範囲で選
ばれる。このモル比が0.１／１００未満では、反応速度
やビスフェノールＡの選択率の向上効果が充分に発揮さ
れないし、また、２０／１００を超えると、その量の割
には効果の向上はあまり認められない。In the present invention, a raw material mixture containing phenol and acetone is continuously supplied to a multi-stage reactor in which at least two reactors filled with a cation exchange resin as a catalyst are arranged in series to carry out the reaction. To do this, a fixed bed multistage continuous reaction system is used. In addition to phenol and acetone, if desired, a promoter may be added to the raw material mixture for the purpose of increasing the selectivity and the reaction rate. Examples of the promoter include alkyl mercaptans such as methyl mercaptan, ethyl mercaptan and n-octyl mercaptan, thiocarboxylic acids such as thioglycolic acid and β-mercaptopropionic acid, aminoalkanethiols such as 2-aminoethanethiol, Examples thereof include mercapto alcohols such as mercaptoethanol.
Further, the acetone / phenol molar ratio is usually 1/30 to
It is selected in the range of 1/3, preferably 1/15 to 1/5. If this molar ratio is less than 1/30, the reaction rate will be too slow, and if it exceeds 1/3, the production of impurities will increase and the selectivity of bisphenol A will decrease. On the other hand, the promoter / acetone molar ratio is usually 0.1 / 100 to 20 /
It is selected in the range of 100, preferably 1/10 to 10/100. If the molar ratio is less than 0.1 / 100, the effect of improving the reaction rate and the selectivity of bisphenol A is not sufficiently exerted, and if it exceeds 20/100, the effect is not so improved relative to the amount. unacceptable.
【０００６】触媒の陽イオン交換樹脂としては、スルホ
ン酸系陽イオン交換樹脂が好ましく用いられる。このス
ルホン酸系陽イオン交換樹脂としては、スルホン酸基を
有する強酸性陽イオン交換樹脂であればよく、その具体
例としては、スルホン化スチレン・ジビニルベンゼンコ
ポリマー、スルホン化架橋スチレンポリマー、フェノー
ルホルムアルデヒド−スルホン酸樹脂及びベンゼンホル
ムアルデヒド−スルホン酸樹脂などが挙げられる。これ
らはその一種を単独で使用することもできるし、また、
その二種以上を併用することもできる。As the cation exchange resin for the catalyst, a sulfonic acid cation exchange resin is preferably used. The sulfonic acid-based cation exchange resin may be a strong acid cation exchange resin having a sulfonic acid group, and specific examples thereof include sulfonated styrene / divinylbenzene copolymer, sulfonated crosslinked styrene polymer, phenol formaldehyde- Examples thereof include sulfonic acid resins and benzeneformaldehyde-sulfonic acid resins. These can be used alone, or
Two or more of them can be used in combination.
【０００７】本発明においては、反応温度は、通常、４
０〜１５０℃、好ましくは６０〜１１０℃の範囲で選ば
れる。反応温度が４０℃未満では、反応速度が遅い上
に、反応液の粘度が極めて高く、場合によっては固化す
る恐れがある。また、１５０℃を超えると、反応制御が
困難となり、かつビスフェノールＡの選択率が低下する
上に、触媒の陽イオン交換樹脂が分解又は劣化すること
がある。また、液時空間速度（ＬＨＳＶ）は、通常、0.
２〜３０ｈｒ-1、好ましくは0.５〜６ｈｒ-1の範囲で選
ばれる。さらに、アセトン及び助触媒の反応器への供給
方法については、特に制限はなく、最前段に一括供給し
てもよいし、あるいは各反応器へ分割供給してもよい。In the present invention, the reaction temperature is usually 4
It is selected in the range of 0 to 150 ° C, preferably 60 to 110 ° C. When the reaction temperature is lower than 40 ° C., the reaction rate is slow, and the viscosity of the reaction solution is extremely high, which may cause solidification in some cases. On the other hand, when the temperature exceeds 150 ° C., the reaction control becomes difficult, the selectivity of bisphenol A decreases, and the cation exchange resin of the catalyst may decompose or deteriorate. The liquid hourly space velocity (LHSV) is usually 0.
It is selected in the range of 2 to 30 hr -1 , preferably 0.5 to 6 hr -1 . Furthermore, the method of supplying acetone and the cocatalyst to the reactor is not particularly limited, and they may be supplied all at once at the front stage, or may be separately supplied to each reactor.
【０００８】本発明においては、触媒の劣化がより進行
した陽イオン交換樹脂を新たな又は再生した陽イオン交
換樹脂と交換する場合、該新たな又は再生した陽イオン
交換樹脂を充填した反応器を、反応系の後段に設置する
ことが必要である。反応系の前段に設置した場合、触媒
が有効に利用されず、反応器トータルでのビスフェノー
ルＡの収率が低下するとともに、触媒の劣化も速くな
る。通常、多段反応器においては、前段の反応器ほど触
媒の劣化が大きいので、特に第１段目の反応器を取り除
き、新たな又は再生した陽イオン交換樹脂を充填した反
応器を最後段に設置するのが有利である。In the present invention, when the cation exchange resin in which the deterioration of the catalyst is more advanced is replaced with a new or regenerated cation exchange resin, a reactor filled with the new or regenerated cation exchange resin is used. , It is necessary to install it in the latter stage of the reaction system. When installed in the preceding stage of the reaction system, the catalyst is not effectively used, the yield of bisphenol A in the total reactor is lowered, and the deterioration of the catalyst is accelerated. Usually, in a multi-stage reactor, the deterioration of the catalyst is larger than that of the previous stage reactor, so the first stage reactor is removed in particular and a reactor filled with new or regenerated cation exchange resin is installed in the last stage. Is advantageous.
【０００９】図１は、本発明の方法を実施するための一
例の説明図であって、（Ａ）は、フェノール及びアセト
ンを含む原料混合物を第１段目の反応器１に供給し、順
次第２段目の反応器２、・・・・、第ｎ段目の反応器ｎ
に流していく反応様式を示す。（Ｂ）は、触媒の劣化が
最も大きい第１段目の反応器１を取り除き、最後段に新
品（又は再生）の陽イオン交換樹脂を充填した反応器を
設置し、原料混合物を最前段の反応器２に供給し、順次
反応器３、・・・、反応器ｎ、新品触媒反応器えと流し
ていく反応様式を示す。このようにして、多段反応器か
ら出てきた反応混合物は、公知の方法により後処理が施
され、ビスフェノールＡが取り出される。FIG. 1 is an explanatory view of an example for carrying out the method of the present invention. In FIG. 1 (A), a raw material mixture containing phenol and acetone is fed to a reactor 1 of the first stage, and then sequentially. 2nd stage reactor 2, ..., Reactor n of nth stage
It shows the reaction mode of flowing into. In (B), the first-stage reactor 1 in which the catalyst is most deteriorated is removed, and a reactor filled with a new (or regenerated) cation exchange resin is installed in the last stage, and the raw material mixture is added to the front stage. The reaction mode is shown in which the reactor 2 is supplied and then sequentially flowed to the reactor 3, ..., Reactor n, and new catalyst reactor. In this way, the reaction mixture discharged from the multistage reactor is subjected to post-treatment by a known method to take out bisphenol A.
【００１０】次に、この後処理の一例について説明す
る。まず、晶析に先立って濃縮を行う。濃縮条件につい
ては、特に制限はないが、通常、温度１３０〜１７０
℃，圧力１００〜４００ｔｏｒｒの条件で濃縮が行われ
る。温度が１３０℃未満では、高真空が必要となるし、
また、１７０℃を超えると、不純物が増加したり、着色
の原因となる。また、濃縮残液のビスフェノールＡの濃
度は２５〜４０重量％の範囲にあるのが有利である。こ
の濃度が２５重量％未満では、ビスフェノールＡの回収
率が低いし、また、４０重量％を超えると、晶析後のス
ラリーの移送が困難となる。濃縮残液からのビスフェノ
ールＡとフェノールとの付加物の晶析は、通常、冷却晶
析法によって行われる。この際の晶析温度は４０〜７０
℃が好ましい。晶析温度が４０℃未満では、晶析液の粘
度の増大や固化をもたらす恐れがあり、また、７０℃を
超えると、ビスフェノールＡの溶解ロスが大きくなり、
好ましくない。Next, an example of this post-processing will be described. First, concentration is performed prior to crystallization. The concentration condition is not particularly limited, but usually, the temperature is 130 to 170.
Concentration is carried out under conditions of a temperature of 100 to 400 torr. If the temperature is lower than 130 ° C, a high vacuum is required,
On the other hand, if the temperature exceeds 170 ° C., impurities may increase or coloring may occur. Also, the concentration of bisphenol A in the concentrated residual liquid is advantageously in the range of 25 to 40% by weight. If this concentration is less than 25% by weight, the recovery rate of bisphenol A is low, and if it exceeds 40% by weight, it becomes difficult to transfer the slurry after crystallization. Crystallization of an adduct of bisphenol A and phenol from the concentrated residual liquid is usually performed by a cooling crystallization method. The crystallization temperature at this time is 40 to 70.
C is preferred. If the crystallization temperature is lower than 40 ° C, the crystallization liquid may increase in viscosity or solidify, and if it exceeds 70 ° C, the bisphenol A dissolution loss becomes large.
Not preferable.
【００１１】次いで、このようにして晶析されたビスフ
ェノールＡとフェノールとの付加物は、公知の方法によ
り分離したのち、通常、フェノールにより洗浄処理が施
される。続いて、洗浄処理された付加物をビスフェノー
ルＡとフェノールとに分解処理するが、この場合、温度
は通常１３０〜２００℃、好ましくは１５０〜１８０℃
の範囲で選ばれ、一方、圧力は通常２０〜１５０ｔｏｒ
ｒの範囲で選ばれる。この分解処理により得られたビス
フェノールＡは、その中の残留フェノールをスチームス
トリッピングなどの方法により、実質上完全に除去する
ことによって、高品質のビスフェノールＡが得られる。Next, the bisphenol A-phenol adduct thus crystallized is separated by a known method, and then usually washed with phenol. Subsequently, the washed adduct is decomposed into bisphenol A and phenol, in which case the temperature is usually 130 to 200 ° C, preferably 150 to 180 ° C.
The pressure is usually 20 to 150 torr.
It is selected within the range of r. In the bisphenol A obtained by this decomposition treatment, residual phenol in the bisphenol A can be substantially completely removed by a method such as steam stripping to obtain high quality bisphenol A.
【００１２】[0012]
【実施例】次に、本発明を実施例および比較例により、
さらに詳しく説明するが、本発明はこれらの例によって
なんら限定されるものではない。 参考例１ 予めフェノールで膨潤させた陽イオン交換樹脂〔スルホ
ン化スチレン−ジビニルベンゼンコポリマー，三菱化成
（株）製、商品名：ダイヤイオンＳＫ−１０４Ｈ〕７4.
４ミリリットルを充填した固定床（1.３ｃｍφ×５6.１
ｃｍ）２基を連結した連続二段反応器を用い、第１段目
の反応器にフェノール4.６８モル／時間を、第１段目及
び第２段目の反応器に、それぞれアセトン0.１５６モル
／時間とアセトンに溶解したエチルメルカプタン0.００
７８モル／時間を通液して、連続反応を行った。反応混
合物を経時的に分析し、フェノール転化率を求めたとこ
ろ、反応開始時に第１段目反応器6.０％，第２段目反応
器１0.６％であったものが、8,０００時間通液後には、
それぞれ0.９％、8.０％となった。EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
As will be described in more detail, the present invention is in no way limited by these examples. Reference Example 1 Cation exchange resin [sulfonated styrene-divinylbenzene copolymer, manufactured by Mitsubishi Kasei Co., Ltd., trade name: Diaion SK-104H] swollen with phenol in advance 74.
Fixed bed filled with 4 ml (1.3 cmφ × 56.1
cm) using a continuous two-stage reactor in which two groups were connected, 4.68 mol / hour of phenol was added to the first-stage reactor, and acetone was added to each of the first- and second-stage reactors at an amount of 0. Ethyl mercaptan 0.000 dissolved in acetone at 156 mol / hr
A continuous reaction was carried out by passing 78 mol / hour. When the reaction mixture was analyzed over time and the conversion of phenol was determined, it was found that the first stage reactor was 6.0% and the second stage reactor was 10.6% at the start of the reaction. After passing the time,
They were 0.9% and 8.0%, respectively.
【００１３】実施例１ より劣化の大きい第１段目反応器を新品触媒に交換する
際に、この新品触媒を充填した反応器を最後段（第２段
目）反応器に、それまでの第２段目反応器を最前段（第
１段目）反応器として使用したとき、フェノール転化率
は第１段目及び第２段目反応器で、それぞれ4.３％、9.
９％となった。Example 1 When replacing the first-stage reactor, which is more deteriorated, with a new catalyst, the reactor filled with this new catalyst was used as the last (second) reactor, and When the second-stage reactor was used as the frontmost (first-stage) reactor, the phenol conversions were 4.3% and 9.% for the first-stage and second-stage reactors, respectively.
It was 9%.
【００１４】比較例１ 実施例１において、最も劣化の大きい第１段目反応器を
新品触媒に交換する際に、新品触媒を充填した反応器を
そのまま第１段目の反応器とし、それまでの第２段目の
反応器もそのまま第２段目反応器として使用した以外
は、実施例１と同様に行った。その結果、フェノール転
化率は第１段目及び第２段目反応器で、それぞれ6.０
％、8.８％となった。Comparative Example 1 In Example 1, when the first-stage reactor with the largest deterioration was replaced with a new catalyst, the reactor filled with the new catalyst was directly used as the first-stage reactor. Example 1 was repeated except that the second-stage reactor of was also used as it was as the second-stage reactor. As a result, the phenol conversion was 6.0 in each of the first and second stage reactors.
% And 8.8%.
【００１５】[0015]
【発明の効果】以上の如く、本発明によれば、触媒とし
て陽イオン交換樹脂を用いて、連続的にビスフェノール
Ａを製造するに際して、ビスフェノールＡの収率を向上
させ得るとともに、該陽イオン交換樹脂の寿命を延長さ
せることができる。As described above, according to the present invention, when continuously producing bisphenol A using a cation exchange resin as a catalyst, the yield of bisphenol A can be improved, and the cation exchange resin can be improved. The life of the resin can be extended.
【図１】 本発明の方法を実施するための一例の説明図
である。FIG. 1 is an illustration of an example for carrying out the method of the present invention.
Claims (2)
少なくとも２基の反応器が直列に配置された多段反応器
に、フェノールとアセトンとを含む原料混合物を連続的
に供給して２，２−ビス（４−ヒドロキシフェニル）プ
ロパンを製造する方法において、触媒劣化のより進行し
た陽イオン交換樹脂に代えて、新たな又は再生した陽イ
オン交換樹脂を反応に供するに当たり、該新たな又は再
生した陽イオン交換樹脂を充填した反応器を反応系の後
段に設置することを特徴とする２，２−ビス（４−ヒド
ロキシフェニル）プロパンの製造方法。1. A raw material mixture containing phenol and acetone is continuously fed to a multistage reactor in which at least two reactors filled with a cation exchange resin as a catalyst are arranged in series, In the method for producing bis (4-hydroxyphenyl) propane, when a new or regenerated cation exchange resin is used in the reaction instead of the cation exchange resin with more advanced catalyst deterioration, the new or regenerated cation exchange resin is used. A method for producing 2,2-bis (4-hydroxyphenyl) propane, characterized in that a reactor filled with an ion exchange resin is installed in the latter stage of the reaction system.
た陽イオン交換樹脂に代えて、新たな又は再生した陽イ
オン交換樹脂を反応に供するに当たり、該新たな又は再
生した陽イオン交換樹脂を充填した反応器を反応系の最
後段に設置することを特徴とする請求項１記載の２，２
−ビス（４−ヒドロキシフェニル）プロパンの製造方
法。2. When a new or regenerated cation exchange resin is used in the reaction in place of the cation exchange resin packed in the first stage where the catalyst deterioration has progressed, the new or regenerated cation exchange resin is used. 2. The reactor according to claim 1, wherein the reactor filled with the resin is installed at the last stage of the reaction system.
-A method for producing bis (4-hydroxyphenyl) propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18089292A JP3748574B2 (en) | 1992-07-08 | 1992-07-08 | Method for producing 2,2-bis (4-hydroxyphenyl) propane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18089292A JP3748574B2 (en) | 1992-07-08 | 1992-07-08 | Method for producing 2,2-bis (4-hydroxyphenyl) propane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625042A true JPH0625042A (en) | 1994-02-01 |
| JP3748574B2 JP3748574B2 (en) | 2006-02-22 |
Family
ID=16091156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18089292A Expired - Lifetime JP3748574B2 (en) | 1992-07-08 | 1992-07-08 | Method for producing 2,2-bis (4-hydroxyphenyl) propane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3748574B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855606A (en) * | 1987-08-12 | 1989-08-08 | Oberg Industries, Inc. | Method and apparatus for detecting a misfeed in a stamping press |
| WO2002072515A1 (en) * | 2001-03-08 | 2002-09-19 | Idemitsu Petrochemical Co., Ltd. | Method for producing bisphenol a |
| WO2002085830A1 (en) * | 2001-04-17 | 2002-10-31 | Idemitsu Petrochemical Co., Ltd. | Process for producing bisphenol a |
| JP2003160533A (en) * | 2001-11-28 | 2003-06-03 | Mitsubishi Rayon Co Ltd | Reactor and method for producing ester |
-
1992
- 1992-07-08 JP JP18089292A patent/JP3748574B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855606A (en) * | 1987-08-12 | 1989-08-08 | Oberg Industries, Inc. | Method and apparatus for detecting a misfeed in a stamping press |
| WO2002072515A1 (en) * | 2001-03-08 | 2002-09-19 | Idemitsu Petrochemical Co., Ltd. | Method for producing bisphenol a |
| US6727394B2 (en) | 2001-03-08 | 2004-04-27 | Idemitsu Petrochemical Co., Ltd. | Method for producing bisphenol A |
| KR100847190B1 (en) * | 2001-03-08 | 2008-07-17 | 이데미쓰 고산 가부시키가이샤 | Manufacturing method of bisphenol A |
| WO2002085830A1 (en) * | 2001-04-17 | 2002-10-31 | Idemitsu Petrochemical Co., Ltd. | Process for producing bisphenol a |
| JP2003160533A (en) * | 2001-11-28 | 2003-06-03 | Mitsubishi Rayon Co Ltd | Reactor and method for producing ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3748574B2 (en) | 2006-02-22 |
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