JP2002265403A - Method for producing bisphenol a - Google Patents
Method for producing bisphenol aInfo
- Publication number
- JP2002265403A JP2002265403A JP2001064671A JP2001064671A JP2002265403A JP 2002265403 A JP2002265403 A JP 2002265403A JP 2001064671 A JP2001064671 A JP 2001064671A JP 2001064671 A JP2001064671 A JP 2001064671A JP 2002265403 A JP2002265403 A JP 2002265403A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- exchange resin
- sulfonic acid
- ion exchange
- washing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 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 78
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 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 65
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 59
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 59
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000005406 washing Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 239000003729 cation exchange resin Substances 0.000 abstract description 7
- 150000002500 ions Chemical group 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- -1 alkyl mercaptans Chemical class 0.000 description 11
- 238000011282 treatment Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical group CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241001550224 Apha Species 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical group OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- SNPQRYOQWLOTFA-UHFFFAOYSA-N 2,2-dimethyl-1,3-thiazolidine Chemical compound CC1(C)NCCS1 SNPQRYOQWLOTFA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 101710142585 50S ribosomal protein 6, chloroplastic Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (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Ａの
製造方法に関し、さらに詳しくは、スルホン酸型イオン
交換樹脂触媒を用いて、フェノールとアセトンからビス
フェノールＡ〔２，２−ビス（４−ヒドロキシフェニ
ル）プロパン〕を製造するに際し、該触媒として、特定
の簡易洗浄法により、洗浄に要する時間の短いものを選
別して使用するビスフェノールＡの製造方法に関するも
のである。The present invention relates to a method for producing bisphenol A, and more particularly, to bisphenol A [2,2-bis (4-hydroxyphenyl) from phenol and acetone using a sulfonic acid type ion exchange resin catalyst. The present invention relates to a method for producing bisphenol A, wherein a catalyst requiring a short time for washing is selected and used by a specific simple washing method when producing propane.
【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。この反応における酸触媒と
しては、従来、硫酸や塩化水素などの無機鉱酸が用いら
れていたが、近年、陽イオン交換樹脂が注目され（英国
特許第８４２２０９号明細書、同第８４９５６５号明細
書、同第８８３３９１号明細書）、工業的に用いられる
ようになった。一方、助触媒として用いられる硫黄化合
物としては、メチルメルカプタン、エチルメルカプタ
ン、チオグリコール酸などの置換基を有する若しくは有
しないアルキルメルカプタン類が有効であることが知ら
れている（米国特許第２３５９２４２号明細書、同第２
７７５６２０号明細書）。このメルカプタン類は、反応
速度を上げるとともに、選択率を向上させる作用を有し
ている。例えば、ビスフェノールＡの製造において、反
応副生物として、主に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（ｏ，ｐ’
一体）が生成し、その他トリスフェノール、ポリフェノ
ールなどが生成する。特に、ポリカーボネート樹脂やポ
リアリレート樹脂などの原料として用いる場合、これら
の副生物の含有量が少なく、着色のない高純度のビスフ
ェノールＡが要求される。このため、反応速度を上げる
とともに、上記副生物の生成を抑え、選択率を高めるた
めに、助触媒としてメルカプタン類が用いられる。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 bisphenol A has been increasing in recent years. This bisphenol A is produced by condensing excess phenol with acetone in the presence of an acidic catalyst and optionally a cocatalyst such as a sulfur compound. Conventionally, inorganic mineral acids such as sulfuric acid and hydrogen chloride have been used as the acid catalyst in this reaction, but cation exchange resins have recently attracted attention (UK Patent Nos. 842209 and 848565). No. 883391), which has been used industrially. On the other hand, it is known that alkyl mercaptans having or not having a substituent such as methyl mercaptan, ethyl mercaptan, and thioglycolic acid are effective as sulfur compounds used as a cocatalyst (US Pat. No. 2,359,242). Book, 2nd
775620). These mercaptans have the effect of increasing the reaction rate and increasing the selectivity. For example, in the production of bisphenol A, 2- (2-hydroxyphenyl) is mainly used as a reaction by-product.
-2- (4-hydroxyphenyl) propane (o, p '
) And other trisphenols and polyphenols. In particular, when used as a raw material such as a polycarbonate resin or a polyarylate resin, bisphenol A having a low content of these by-products and a high purity without coloring is required. For this reason, mercaptans are used as a co-catalyst in order to increase the reaction rate, suppress the generation of the by-products, and increase the selectivity.
【０００３】フェノールとアセトンを縮合させてビスフ
ェノールＡを工業的に製造する場合、一般に、前記陽イ
オン交換樹脂を充填した反応塔に、原料のフェノールと
アセトン及び助触媒のメルカプタン類を連続的に供給す
る固定床連続反応方式が採用される。この固定床連続反
応方式においては、通常該陽イオン交換樹脂を充填した
反応基を２基以上直列に連結した固定床多段式反応装置
が用いられる。また、陽イオン交換樹脂としては、触媒
活性などの点から、強酸性のスルホン酸型イオン交換樹
脂が多用されている。When bisphenol A is produced industrially by condensing phenol and acetone, generally, phenol and acetone as raw materials and mercaptans as cocatalysts are continuously supplied to a reaction column filled with the cation exchange resin. A fixed bed continuous reaction system is adopted. In this fixed bed continuous reaction system, a fixed bed multistage reaction apparatus in which two or more reactive groups filled with the cation exchange resin are connected in series is usually used. As the cation exchange resin, a strongly acidic sulfonic acid-type ion exchange resin is frequently used from the viewpoint of catalytic activity and the like.
【０００４】しかしながら、このスルホン酸型イオン交
換樹脂を触媒とした場合、反応開始後に該イオン交換樹
脂からスルホン酸の脱離が起こり、反応液中に溶出した
スルホン酸が、後の工程で高温に曝された際に、ビスフ
ェノールＡの分解を引き起こし、着色した副生物を生成
することが知られている。この着色不純物は、製品ビス
フェノールＡの色相を悪化させるなど、好ましくない事
態を招来するため、特に光ディスクや光ファイバーなど
の光学部材の素材として用いられるポリカーボネート樹
脂向けのビスフェノールＡにおいては、これらの着色不
純物を可及的に低減し、着色のない色相の良好なものが
求められている。したがって、該スルホン酸型イオン交
換樹脂の前処理として、これまで様々な洗浄方法が試み
られている。例えば洗液の比伝導率が、２５℃で約５０
μΩ-1／ｃｍ未満になるまで触媒を脱イオン水で洗浄
し、次いで洗浄したイオン交換樹脂を脱水処理する方法
（特開平９−１７３８５８号公報）、酸性陽イオン交換
樹脂を水、次いでフェノールで洗浄する方法（特開平９
−１７６０６９号公報）、スルホン酸型イオン交換樹脂
を反応器に充填後、該スルホン酸型イオン交換樹脂の水
洗を、洗浄廃水のｐＨが６以上になるまで行い、 次いで
フェノール洗浄を、洗浄フェノール中の脱離スルホン酸
濃度が２重量ｐｐｍ以下になるまで行う方法（特開２０
００−１４３５６５号公報）などが開示されている。However, when this sulfonic acid type ion exchange resin is used as a catalyst, sulfonic acid is desorbed from the ion exchange resin after the start of the reaction, and the sulfonic acid eluted in the reaction solution is heated to a high temperature in a later step. It is known that when exposed, it causes the decomposition of bisphenol A and produces colored by-products. This coloring impurity causes undesirable situations such as deterioration of the hue of the product bisphenol A. In particular, bisphenol A for polycarbonate resin used as a material for optical members such as optical discs and optical fibers is characterized by these coloring impurities. There is a demand for a color which is reduced as much as possible and has a good hue without coloring. Therefore, various preparative treatments have been attempted as a pretreatment of the sulfonic acid type ion exchange resin. For example, the specific conductivity of the washing solution is about 50 at 25 ° C.
A method in which the catalyst is washed with deionized water until it becomes less than μΩ −1 / cm, and then the washed ion-exchange resin is dehydrated (Japanese Patent Application Laid-Open No. 9-173858). Cleaning method (Japanese Unexamined Patent Application Publication No.
After filling the reactor with the sulfonic acid type ion exchange resin, the sulfonic acid type ion exchange resin was washed with water until the pH of the washing wastewater became 6 or more. Until the concentration of desorbed sulfonic acid becomes 2 ppm by weight or less (JP-A-20
No. 00-143565).
【０００５】このように、酸型陽イオン交換樹脂の場
合、水洗浄及びフェノール洗浄が有効であることは公知
であり、この洗浄を充分に行うことにより、触媒充填又
は交換後の製品の色相を良好に維持し得ることも公知で
ある。しかしながら、現状では、触媒を反応器に充填し
たのち、水洗浄及びフェノール洗浄に非常に時間がかか
り、経済性が著しく損なわれるという事態が発生してい
る。例えば湿潤状態で長期間空気中で保存されていたス
ルホン酸型イオン交換樹脂では、その表面及び細孔内部
に、ポリスチレンスルホン酸からなる着色した溶出物が
発生し、洗浄に長時間を要する。したがって、スルホン
酸型イオン交換樹脂を流通式反応器に充填する前に、簡
易的に該樹脂の洗浄性能、すなわち水洗浄及びフェノー
ル洗浄にどの程度の時間を要するかを見極めることが必
要とされている。As described above, in the case of an acid-type cation exchange resin, it is known that water washing and phenol washing are effective, and by sufficiently performing this washing, the hue of the product after catalyst filling or exchange is changed. It is also known that it can be maintained well. However, under the present circumstances, after filling the reactor with the catalyst, it takes a very long time for water washing and phenol washing, and a situation occurs in which economic efficiency is significantly impaired. For example, in the case of a sulfonic acid type ion exchange resin that has been stored in the air in a wet state for a long period of time, a colored eluate composed of polystyrenesulfonic acid is generated on the surface and inside the pores, and it takes a long time to wash. Therefore, before filling the sulfonic acid type ion exchange resin into the flow reactor, it is necessary to simply determine the washing performance of the resin, that is, how much time is required for water washing and phenol washing. I have.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、このような
状況下で、スルホン酸型イオン交換樹脂触媒を用い、フ
ェノールとアセトンからビスフェノールＡを製造するに
際し、該触媒として、簡易洗浄法により、洗浄に要する
時間の短いスルホン酸型イオン交換樹脂を選別して使用
するビスフェノールＡの製造方法を提供することを目的
とするものである。SUMMARY OF THE INVENTION The present invention relates to a method for producing bisphenol A from phenol and acetone using a sulfonic acid type ion exchange resin catalyst under such circumstances. An object of the present invention is to provide a method for producing bisphenol A in which a sulfonic acid type ion exchange resin requiring a short time for washing is selected and used.
【０００７】[0007]
【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結果、スルホン酸型
イオン交換樹脂を、イオン交換水とフェノールを用いる
特定の簡易洗浄法により、洗浄処理を行い、最終的に得
られる洗浄フェノール中の硫黄分濃度が１重量ｐｐｍ以
下であるスルホン酸型イオン交換樹脂を、触媒として用
いることにより、その目的を達成し得ることを見出し
た。本発明は、かかる知見に基づいて完成したものであ
る。すなわち、本発明は、スルホン酸型イオン交換樹脂
を触媒とし、かつメルカプタン類を助触媒として、フェ
ノールとアセトンを縮合させてビスフェノールＡを製造
するに当たり、 上記スルホン酸型イオン交換樹脂とし
て、スルホン酸型イオン交換樹脂を、その水膨潤容積の
５〜２０倍容量のイオン交換水で洗浄したのち、該水膨
潤容積の１〜３倍容量のフェノール中にて５０〜８０℃
の温度で２〜５時間攪拌洗浄し、固液分離後の洗浄フェ
ノール中の硫黄濃度が１重量ｐｐｍ以下であるものを用
い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 intensive studies to achieve the above object, and as a result, the sulfonic acid type ion-exchange resin was purified by a specific simple washing method using ion-exchanged water and phenol. It has been found that the object can be achieved by performing a washing treatment and using a sulfonic acid type ion exchange resin having a sulfur content of 1 ppm by weight or less in a finally obtained washed phenol as a catalyst. The present invention has been completed based on such findings. That is, in the present invention, when a sulfonic acid type ion exchange resin is used as a catalyst, and mercaptans are used as cocatalysts to condense phenol and acetone to produce bisphenol A, the sulfonic acid type ion exchange resin is used as the sulfonic acid type ion exchange resin. After washing the ion-exchange resin with ion-exchanged water having a volume of 5 to 20 times the water swelling volume, the resin is washed with phenol having a volume of 1 to 3 times the water swelling volume at 50 to 80 ° C
And washing with stirring at a temperature of 2 to 5 hours, and using a phenol having a sulfur concentration of 1 ppm by weight or less in the washed phenol after solid-liquid separation.
【０００８】[0008]
【発明の実施の形態】本発明の方法は、スルホン酸型イ
オン交換樹脂を触媒とし、かつメルカプタン類を助触媒
として、フェノールとアセトンを縮合させてビスフェノ
ールＡを製造する方法であって、該スルホン酸型イオン
交換樹脂については、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特に制限されず、例えばスル
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、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。これらはそれぞれ単独で
用いてもよく、二種以上を組み合わせて用いてもよい。
本発明におけるフェノールとアセトンとの縮合において
は、 一般に前記のスルホン酸型イオン交換樹脂を充填し
た反応搭に、 フェノールとアセトンとメルカプタン類を
連続的に供給して反応させる固定床連続反応方式が用い
られる。この際、 反応搭は１基でもよく、また２基以上
を直列又は並列に配置してもよいが、 工業的には、 スル
ホン酸型イオン交換樹脂を充填した反応搭を２基以上直
列に連結し、固定床多段連続反応方式を採用するのが、
特に有利である。前記スルホン酸型イオン交換樹脂を触
媒とした場合、「従来の技術」において説明したよう
に、反応開始後に該イオン交換樹脂からスルホン酸の脱
離が起こり、反応液中に溶出したスルホン酸が、後の工
程で高温に曝された際に、ビスフェノールＡの分解を引
き起こし、着色した副生物を生成することから、一般に
該スルホン酸型イオン交換樹脂を反応器に充填後、この
スルホン酸型イオン交換樹脂の水洗を行い、次いでフェ
ノール洗浄する処置がとられる。このような反応器に充
填したスルホン酸型イオン交換樹脂を水洗浄、次いでフ
ェノール洗浄を行う際に、該イオン交換樹脂によって
は、上記洗浄処理に長時間を要し、経済的に不利となる
場合がある。DETAILED DESCRIPTION OF THE INVENTION The process of the present invention is a process for producing bisphenol A by condensing phenol and acetone using a sulfonic acid type ion exchange resin as a catalyst and mercaptans as a co-catalyst. The acid type ion exchange resin is not particularly limited as long as it is a strongly acidic cation exchange resin having a sulfonic acid group, and examples thereof include a sulfonated styrene-divinylbenzene copolymer, a sulfonated crosslinked styrene polymer, a phenol formaldehyde-sulfonic acid resin, Benzene formaldehyde-sulfonic acid resin and the like. These may be used alone or in combination of two or more.
In the condensation of phenol and acetone in the present invention, a fixed bed continuous reaction system is generally used in which phenol, acetone and mercaptans are continuously supplied and reacted in a reaction tower filled with the sulfonic acid type ion exchange resin. Can be At this time, the number of reactors may be one, or two or more reactors may be arranged in series or parallel. However, industrially, two or more reactors filled with a sulfonic acid type ion exchange resin are connected in series. The fixed bed multi-stage continuous reaction system
It is particularly advantageous. When the sulfonic acid-type ion exchange resin is used as a catalyst, sulfonic acid is desorbed from the ion exchange resin after the start of the reaction, as described in the “prior art”, and the sulfonic acid eluted in the reaction solution is When exposed to a high temperature in a later step, it causes decomposition of bisphenol A and produces a colored by-product. Therefore, generally, the sulfonic acid type ion exchange resin is charged into a reactor, and then the sulfonic acid type ion exchange resin is charged. The resin is washed with water and then treated with phenol. When the sulfonic acid type ion exchange resin filled in such a reactor is washed with water and then with phenol, depending on the ion exchange resin, the above-mentioned washing treatment takes a long time, which is economically disadvantageous. There is.
【０００９】本発明の方法においては、このような事態
に対処するために、以下に示す簡易洗浄法によって、前
記の水、次いでフェノールによる洗浄処理時間が短いス
ルホン酸型イオン交換樹脂を選別して使用する。本発明
におけるこの簡易洗浄法においては、スルホン酸型イオ
ン交換樹脂をその水膨潤容積の５〜２０倍容量のイオン
交換水で洗浄したのち、該水膨潤容積の１〜３倍容量の
フェノール中にて５０〜８０℃の温度で 2〜５時間攪拌
洗浄し、固液分離後の洗浄フェノール中の硫黄濃度が 1
重量ｐｐｍ以下であるスルホン酸型イオン交換樹脂を選
別する。In the method of the present invention, in order to cope with such a situation, a sulfonic acid type ion exchange resin having a short washing time with water and then phenol is selected by a simple washing method described below. use. In this simple washing method of the present invention, the sulfonic acid type ion exchange resin is washed with ion exchange water having a volume of 5 to 20 times its water swelling volume, and then washed with phenol having a volume of 1 to 3 times its water swelling volume. Washing with stirring at a temperature of 50 to 80 ° C for 2 to 5 hours.
A sulfonic acid type ion exchange resin having a weight of not more than ppm is selected.
【００１０】具体的には、まず容器にスルホン酸型イオ
ン交換樹脂を入れ、次いで当該イオン交換樹脂の水膨潤
容積の 2倍容量程度のイオン交換水を加えたのち、攪拌
後、静置し、当該イオン交換樹脂の界面まで上澄み液を
抜く。この操作を使用するイオン交換水の全量が、当該
スルホン酸型イオン交換樹脂の水膨潤容積の５〜２０倍
容量になるまで、複数回繰り返す。このイオン交換水に
よる洗浄処理は、常温、すなわち１０〜３０℃程度の温
度で行う。この際、イオン交換水の全使用量が５倍容量
未満では水による洗浄効果が不充分となり、後の処理で
水で溶出し得るものもフェノールにより溶出し、純粋な
フェノールによる溶出物の測定ができなくなる。また、
２０倍容量より多いと比較する樹脂の間でフェノール洗
浄時の溶出物量の差が表れにくくなる。このようにし
て、イオン交換水による洗浄処理終了後、グラスフィル
ターなどを用いて減圧ろ過したのち、水洗浄スルホン酸
型イオン交換樹脂を再び容器に戻す。次いで、当該スル
ホン酸型イオン交換樹脂の水膨潤容積の１〜３倍容量の
フェノールを加え、５０〜８０℃の温度で２〜５時間攪
拌洗浄する。次いで静置後、上澄みフェノール中の硫黄
濃度を測定し、この値が１重量ｐｐｍ以下であるスルホ
ン酸型イオン交換樹脂を触媒として使用する。Specifically, first, a sulfonic acid type ion exchange resin is put into a container, and then ion exchange water having a volume about twice as large as the water swelling volume of the ion exchange resin is added. The supernatant is drained to the interface of the ion exchange resin. This operation is repeated a plurality of times until the total amount of ion-exchanged water used reaches 5 to 20 times the water swelling volume of the sulfonic acid type ion-exchange resin. This cleaning treatment with ion-exchanged water is performed at normal temperature, that is, at a temperature of about 10 to 30 ° C. At this time, if the total amount of ion-exchanged water is less than 5 times the volume, the washing effect with water will be insufficient, and what can be eluted with water in the subsequent treatment will be eluted with phenol, and the measurement of the eluted material with pure phenol will be impossible. become unable. Also,
If the volume is more than 20 times the volume, the difference in the amount of eluted material during phenol washing between resins to be compared hardly appears. After the washing process with ion-exchanged water is completed in this way, the solution is filtered under reduced pressure using a glass filter or the like, and then the water-washed sulfonic acid-type ion-exchange resin is returned to the container. Next, phenol having a volume of 1 to 3 times the water swelling volume of the sulfonic acid type ion exchange resin is added, and the mixture is washed with stirring at a temperature of 50 to 80 ° C for 2 to 5 hours. Then, after standing, the sulfur concentration in the supernatant phenol is measured, and a sulfonic acid type ion exchange resin having this value of 1 ppm by weight or less is used as a catalyst.
【００１１】この際、フェノールの使用量が１倍容量よ
りも少ないと、フェノールによる樹脂の洗浄が充分に行
われにくい上、上澄みの採取に際し、樹脂の微粒子が取
り込まれる場合がある。また３倍容量より多いと、比較
する樹脂の間で、フェノール洗浄時の溶出物量の差が表
れにくい。次に、本発明の方法において、前記のスルホ
ン酸型イオン交換樹脂を触媒とし、かつメルカプタン類
を助触媒として、フェノールとアセトンを縮合させて、
ビスフェノールＡを製造する方法について説明する。At this time, if the amount of the phenol used is less than 1 volume, it is difficult to sufficiently wash the resin with the phenol, and fine particles of the resin may be taken in when collecting the supernatant. On the other hand, if the volume is more than three times the volume, the difference in the amount of eluted material during phenol washing between the resins to be compared hardly appears. Next, in the method of the present invention, the sulfonic acid type ion exchange resin is used as a catalyst, and mercaptans are used as cocatalysts to condense phenol and acetone,
A method for producing bisphenol A will be described.
【００１２】本発明において用いられるメルカプタン類
は、分子内にＳＨ基を遊離の形で有する化合物であっ
て、このようなものとしては、アルキルメルカプタン
や、カルボキシル基、アミノ基、ヒドロキシル基などの
置換基一種以上を有するアルキルメルカプタン類、例え
ばメルカプトカルボン酸、アミノアルカンチオール、メ
ルカプトアルコールなどを用いることができる。このよ
うなメルカプタン類の例としては、メチルメルカプタ
ン、エチルメルカプタン、ｎ−ブチルメルカプタン、ｎ
−オクチルメルカプタンなどのアルキルメルカプタン，
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、２−アミノエタンチオール、２，２−
ジメチルチアゾリジンなどのアミノアルカンチオール、
メルカプトエタノールなどのメルカプトアルコールなど
が挙げられるが、これらの中で、アルキルメルカプタン
が助触媒としての効果の点で、特に好ましい。また、こ
れらのメルカプタン類は、単独で用いてもよく、二種以
上を組み合わせて用いてもよい。これらのメルカプタン
類は、前記スルホン酸型イオン交換樹脂上に固定化さ
せ、助触媒として機能させることもできる。前記メルカ
プタン類の使用量は、一般に原料のアセトンに対して、
０．１〜２０モル％、好ましくは、１〜１０モル％の範
囲で選定される。The mercaptans used in the present invention are compounds having an SH group in the molecule in a free form, such as alkyl mercaptans, substituted compounds such as carboxyl, amino and hydroxyl groups. Alkyl mercaptans having one or more groups, for example, mercaptocarboxylic acid, aminoalkanethiol, mercaptoalcohol and the like can be used. Examples of such mercaptans include methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, n
Alkyl mercaptans such as octyl mercaptan,
Thiocarboxylic acids such as thioglycolic acid and β-mercaptopropionic acid, 2-aminoethanethiol, 2,2-
Aminoalkanethiols such as dimethylthiazolidine,
Examples thereof include mercapto alcohols such as mercaptoethanol, and among them, alkyl mercaptans are particularly preferable in view of the effect as a cocatalyst. Further, these mercaptans may be used alone or in combination of two or more. These mercaptans can also be immobilized on the sulfonic acid type ion exchange resin and function as a cocatalyst. The amount of the mercaptans used is generally based on acetone as a raw material.
It is selected in the range of 0.1 to 20 mol%, preferably 1 to 10 mol%.
【００１３】また、フェノールとアセトンとの使用割合
については特に制限はないが、生成するビスフェノール
Ａの精製の容易さや経済性などの点から、未反応のアセ
トンの量は出来るだけ少ないことが望ましく、したがっ
て、フェノールを化学量論的量よりも過剰に用いるのが
有利である。通常、アセトン１モル当たり、３〜３０モ
ル、好ましくは５〜１５モルのフェノールが用いられ
る。また、このビスフェノールＡの製造においては、反
応溶媒は、反応液の粘度が高すぎたり、凝固して運転が
困難になるような低温で反応させる以外は、一般に必要
ではない。The proportion of phenol and acetone used is not particularly limited, but the amount of unreacted acetone is desirably as small as possible from the viewpoints of easiness of purification of bisphenol A and economical efficiency. Therefore, it is advantageous to use phenol in excess of the stoichiometric amount. Usually, 3 to 30 moles, preferably 5 to 15 moles, of phenol are used per mole of acetone. In the production of bisphenol A, a reaction solvent is generally not necessary, except that the reaction solution has a too high viscosity or reacts at a low temperature at which the operation is difficult due to solidification.
【００１４】本発明においては、前述の簡易洗浄法によ
り選別された、触媒洗浄に要する時間が短いスルホン酸
型イオン交換樹脂を充填した反応搭に、フェノールとア
セトンと前記メルカプタン類を連続的に供給して反応さ
せる固定床連続反応方式が用いられる。 本発明におい
ては、 反応に先立ち、 反応搭に充填されたスルホン酸型
イオン交換樹脂の洗浄処理を行う。この洗浄では、まず
スルホン酸型イオン交換樹脂が充填された反応搭に水を
流して、 洗浄廃水のｐＨが５．５〜７程度になるまで水
洗浄を行う。次いで、 反応搭のイオン交換樹脂温度を５
０〜８０℃程度に保持しながらフェノールを流し、 該ス
ルホン酸型イオン交換樹脂中の水をフェノールで置換す
ると共に、 フェノール洗浄を、 洗浄フェノール中の硫黄
濃度が１重量ｐｐｍ以下になるまで行う。次に、 反応搭
にフェノールとアセトンとメルカプタン類を連続的に供
給して、固定床連続反応方式により、 反応を行う。この
固定床連続反応方式における反応条件について説明す
る。まず、アセトン／フェノールモル比は、通常１／３
０〜１／３、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より小さい場合、反応速度
が遅くなりすぎるおそれがあり、１／３より大きいと不
純物の生成が多くなり、ビスフェノールＡの選択率が低
下する傾向がある。一方、メルカプタン類がスルホン酸
型イオン交換樹脂に固定化されない場合、メルカプタン
類／アセトンモル比は、通常０．１／１００〜２０／１
００、好ましくは１／１００〜１０／１００の範囲で選
ばれる。このモル比が０．１／１００より小さい場合、
反応速度やビスフェノールＡの選択率の向上効果が十分
に発揮されないおそれがあり、２０／１００より大きい
とその量の割りには効果の向上はあまり認められない。In the present invention, phenol, acetone and the above mercaptans are continuously supplied to a reaction column filled with a sulfonic acid type ion exchange resin which requires a short time for catalyst cleaning and which is selected by the above-mentioned simple cleaning method. A fixed-bed continuous reaction system in which the reaction is carried out is used. In the present invention, prior to the reaction, the sulfonic acid type ion exchange resin charged in the reaction tower is washed. In this washing, first, water is flowed through a reaction tower filled with a sulfonic acid type ion exchange resin, and water washing is performed until the pH of the washing wastewater becomes about 5.5 to 7. Next, the temperature of the ion exchange resin in the reaction tower was set to 5
Phenol is flown while maintaining the temperature at about 0 to 80 ° C., and water in the sulfonic acid type ion exchange resin is replaced with phenol, and phenol washing is performed until the sulfur concentration in the washed phenol becomes 1 ppm by weight or less. Next, phenol, acetone and mercaptans are continuously supplied to the reaction tower, and the reaction is carried out by a fixed bed continuous reaction system. The reaction conditions in this fixed bed continuous reaction system will be described. First, the acetone / phenol molar ratio is usually 1/3.
It is selected in the range of 0 to 1/3, preferably 1/15 to 1/5. If the molar ratio is smaller than 1/30, the reaction rate may be too slow. If the molar ratio is larger than 1/3, the generation of impurities increases, and the selectivity of bisphenol A tends to decrease. On the other hand, when the mercaptans are not immobilized on the sulfonic acid type ion exchange resin, the mercaptans / acetone molar ratio is usually 0.1 / 100 to 20/1.
00, preferably in the range of 1/100 to 10/100. If this molar ratio is less than 0.1 / 100,
There is a possibility that the effect of improving the reaction rate and the selectivity of bisphenol A may not be sufficiently exhibited, and if it is larger than 20/100, the effect is not so much improved in proportion to the amount.
【００１５】また、反応温度は、通常４０〜１５０℃、
好ましくは６０〜１１０℃の範囲で選ばれる。該温度が
４０℃未満では反応速度が遅い上、反応液の粘度が極め
て高く、場合により、固化するおそれがあり、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（ｐ，ｐ’一体）の選択率が低下する上、触媒のスル
ホン酸型イオン交換樹脂が分解又は劣化することがあ
る。さらに、原料混合物のＬＨＳＶ（液空間速度）は、
通常0.２〜３０ｈｒ-1、 好ましくは0.５〜１０ｈｒ-1の
範囲で選ばれる。The reaction temperature is usually 40 to 150 ° C.,
Preferably, it is selected in the range of 60 to 110 ° C. If the temperature is lower than 40 ° C., the reaction rate is low, and the viscosity of the reaction solution is extremely high.
When it exceeds, the reaction control becomes difficult, the selectivity of bisphenol A (p, p 'integrated) decreases, and the sulfonic acid type ion exchange resin of the catalyst may be decomposed or deteriorated. Further, the LHSV (liquid hourly space velocity) of the raw material mixture is
Usually, it is selected in the range of 0.2 to 30 hr -1 , preferably 0.5 to 10 hr -1 .
【００１６】本発明の方法においては、反応塔から出て
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。次に、この後処理の
一例について説明すると、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１
３０〜１７０℃、圧力１３〜５３ｋＰａ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
り、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
く、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
ルの付加物の晶析は、通常減圧下で水の蒸発潜熱を利用
して冷却する真空冷却晶析法によって行われる。この真
空冷却晶析法においては、該濃縮残液に、水を３〜２０
重量％程度添加し、通常温度４０〜７０℃、圧力３〜１
３ｋＰａの条件で晶析処理が行われる。上記水の添加量
が３重量％未満では除熱能力が十分ではなく、２０重量
％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。また晶析温度が４０℃未満では晶析
液の粘度の増大や固化をもたらすおそれがあり、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。In the method of the present invention, the reaction mixture coming out of the reaction tower is subjected to a post-treatment by a known method,
Bisphenol A is removed. Next, an example of this post-treatment will be described. First, concentration is performed prior to crystallization. The concentration conditions are not particularly limited, but are usually at a temperature of 1
The concentration is performed under the conditions of 30 to 170 ° C. and a pressure of 13 to 53 kPa. When the temperature is lower than 130 ° C., a high vacuum is required. Further, the concentration of bisphenol A in the concentrated residue is advantageously in the range of 25 to 40% by weight. If the concentration is less than 25% by weight, the recovery 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 residue is usually carried out by vacuum cooling crystallization in which cooling is performed using the latent heat of evaporation of water under reduced pressure. In this vacuum cooling crystallization method, 3 to 20
% By weight, normal temperature of 40 to 70 ° C, pressure of 3 to 1
The crystallization treatment is performed under the conditions of 3 kPa. If the amount of water is less than 3% by weight, the heat removal ability is not sufficient, and if it exceeds 20% by weight, the dissolution loss of bisphenol A increases, which is not preferable. If the crystallization temperature is lower than 40 ° C., the viscosity of the crystallization liquid may increase or solidify.
If it exceeds 300, the dissolution loss of bisphenol A increases, which is not preferable.
【００１７】次に、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。次いで、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離処理するが、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３〜２０ｋＰａの範囲で選
ばれる。この分離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 thus-crystallized adduct of bisphenol A and phenol is separated by a known method, and is usually washed with phenol. Next, the washed adduct was replaced with bisphenol A.
In this case, the temperature is usually selected in the range of 130 to 200 ° C, preferably 150 to 180 ° C, while the pressure is generally selected in the range of 3 to 20 kPa. Bisphenol A obtained by this separation treatment
In this method, high-quality bisphenol A can be obtained by substantially completely removing residual phenol therein by a method such as steam stripping.
【００１８】[0018]
【実施例】次に、 本発明を実施例により、さらに詳細に
説明するが、本発明は、 この例によってなんら限定され
るものではない。 実施例１ （１）簡易洗浄テスト １００ミリリットル容のサンプル瓶に、スルホン酸型イ
オン交換樹脂を水膨潤容積で５０ミリリットル充填した
後、 イオン交換水を、 該樹脂を含めた総容積が１００ミ
リリットルになるまで加えた。次いで、 攪拌したのち、
静置し、樹脂の界面まで上澄みを抜いた。この操作を１
０回繰り返したのち、グラスフィルターを用い、アスピ
レーターで減圧ろ過し、 概略水を切った。このスルホン
酸型イオン交換樹脂を、 再び１００ミリリットル容サン
プルびんに戻し、 フェノールを樹脂を含めた総容積が１
００ミリリットルになるまで入れ、７０℃で３時間攪拌
した。攪拌終了後、静置し、 上澄みフェノールを採取
し、硫黄濃度を測定した結果、１重量ｐｐｍ未満であっ
た。 （２）連続流通テスト 上記（１）で用いたものと同じスルホン酸型イオン交換
樹脂７０ミリリットルを、 内径１４ｍｍ、長さ４５０ｍ
ｍのステンレススチール管に充填した。次いで、この反
応器にイオン交換水を１０ミリリットル／ｈで２５時間
連続的に流通させた。２５時間後の洗浄廃水のｐＨを測
定したところ、５．５であり、リトマス試験紙では中性
を示した。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Simple washing test A 100 ml sample bottle was filled with 50 ml of a sulfonic acid type ion exchange resin in a water swelling volume, and then ion exchange water was added to a total volume of 100 ml including the resin. Added until it was. Then, after stirring,
The mixture was allowed to stand, and the supernatant was removed to the resin interface. This operation is 1
After repeating 0 times, the mixture was filtered under reduced pressure with an aspirator using a glass filter, and approximately water was removed. The sulfonic acid type ion exchange resin was returned to the 100 ml sample bottle again, and the total volume of phenol and resin was 1
The mixture was added until the volume reached 00 ml and stirred at 70 ° C. for 3 hours. After the stirring, the mixture was allowed to stand, the supernatant phenol was collected, and the sulfur concentration was measured. The result was less than 1 ppm by weight. (2) Continuous flow test 70 ml of the same sulfonic acid type ion exchange resin as used in the above (1) was used, with an inner diameter of 14 mm and a length of 450 m.
m stainless steel tubes. Next, ion-exchanged water was continuously passed through the reactor at 10 ml / h for 25 hours. When the pH of the washing wastewater after 25 hours was measured, it was 5.5, and the litmus test paper showed neutrality.
【００１９】次に、 樹脂層の温度を７０℃に上げ、フェ
ノールを１０ミリリットル／ｈで２５時間流し、脱水を
行った。２５時間後のフェノール中の水濃度は０. ３重
量％であった。この時点でフェノール中の硫黄濃度とフ
ェノールの色相を測定した結果、硫黄濃度は４重量ｐｐ
ｍで、 色相はＡＰＨＡで３０以上であった。次いで、フ
ェノール洗浄を、上記の脱水条件と同様の条件で行っ
た。このフェノール洗浄を開始してから１０時間後に洗
浄フェノール中の硫黄濃度が１重量ｐｐｍまで低下し
た。この際、 洗浄フェノールの色相はＡＰＨＡで１５で
あった。Next, the temperature of the resin layer was raised to 70 ° C., and phenol was flowed at 10 ml / h for 25 hours to perform dehydration. After 25 hours, the water concentration in the phenol was 0.3% by weight. At this time, the sulfur concentration in the phenol and the hue of the phenol were measured.
m, the hue was 30 or more in APHA. Next, phenol washing was performed under the same conditions as the above-mentioned dehydration conditions. Ten hours after starting the phenol washing, the sulfur concentration in the washed phenol decreased to 1 ppm by weight. At this time, the color of the washed phenol was 15 in APHA.
【００２０】比較例１ (１) 簡易洗浄テスト 実施例１で用いたものと同じスルホン酸型イオン交換樹
脂を、 空気中で２ヶ月間保存したのち、実施例１（１）
と同様な操作を行った。上澄みフェノールを採取して、
硫黄濃度を測定した結果、４重量ｐｐｍであった。 （２）連続流通テスト 上記 (１) で用いたものと同じ空気中で２ヶ月間保持し
たスルホン酸型イオン交換樹脂を用い、 実施例１（２）
と同様な操作を行った。水洗浄２５時間後の洗浄廃水の
ｐＨを測定したところｐＨは５．０であり、リトマス試
験紙では中性を示した。また、 フェノールによる脱水２
５時間後のフェノール中の水濃度は０. ３重量％であっ
た。この時点でフェノール中の硫黄濃度とフェノールの
色相を測定した結果、 硫黄濃度は８重量ppm で、 色相は
ＡＰＨＡで３０以上であった。次いで、フェノール洗浄
を、 上記の脱水条件と同様の条件で行った。このフェノ
ール洗浄を開始してから４０時間後に洗浄フェノール中
の硫黄濃度が１重量ppm まで低下した。この際、 洗浄フ
ェノールの色相はＡＰＨＡで２０であった。実施例１と
比較例１から分かるように、 簡易洗浄テスト結果と連続
流通系での確認結果に相関が見られた。Comparative Example 1 (1) Simple cleaning test The same sulfonic acid type ion exchange resin as used in Example 1 was stored in the air for 2 months, and then was subjected to Example 1 (1).
The same operation as described above was performed. Collect the supernatant phenol,
As a result of measuring the sulfur concentration, it was 4 wt ppm. (2) Continuous flow test Example 1 (2) using a sulfonic acid type ion exchange resin kept in the same air as that used in (1) above for 2 months.
The same operation as described above was performed. When the pH of the washing wastewater after 25 hours of water washing was measured, the pH was 5.0, and the litmus test paper showed neutrality. Dehydration with phenol 2
After 5 hours, the water concentration in the phenol was 0.3% by weight. At this time, the sulfur concentration in the phenol and the hue of the phenol were measured. As a result, the sulfur concentration was 8 ppm by weight, and the hue was 30 or more in APHA. Next, phenol washing was performed under the same conditions as the above-mentioned dehydration conditions. Forty hours after the start of the phenol washing, the sulfur concentration in the washed phenol decreased to 1 ppm by weight. At this time, the color of the washed phenol was 20 in APHA. As can be seen from Example 1 and Comparative Example 1, there was a correlation between the result of the simple cleaning test and the result of confirmation in the continuous flow system.
【００２１】[0021]
【発明の効果】本発明によれば、 スルホン酸型イオン交
換樹脂触媒を用い、フェノールとアセトンからビスフェ
ノールＡを製造するに際し、該触媒として、 特定の簡易
洗浄法により、 洗浄に要する時間の短いスルホン酸型イ
オン交換樹脂を選別して使用することにより、 ビスフェ
ノールA を経済的に有利に製造することができる。According to the present invention, in the production of bisphenol A from phenol and acetone using a sulfonic acid type ion exchange resin catalyst, a sulfone having a short time required for cleaning by a specific simple cleaning method is used as the catalyst. By selectively using an acid-type ion exchange resin, bisphenol A can be produced economically and advantageously.
フロントページの続き Ｆターム(参考） 4G069 AA02 AA08 BA21A BA24A BA24B BE21A CB25 DA05 EC27 FA01 FB27 FC07 FC08 4H006 AA02 AC25 BA52 BA72 BA84 BD36 BD52 DA64 FC52 FE13 FG29 4H039 CA60 CL25 Continued on front page F-term (reference) 4G069 AA02 AA08 BA21A BA24A BA24B BE21A CB25 DA05 EC27 FA01 FB27 FC07 FC08 4H006 AA02 AC25 BA52 BA72 BA84 BD36 BD52 DA64 FC52 FE13 FG29 4H039 CA60 CL25
Claims (1)
し、かつメルカプタン類を助触媒として、フェノールと
アセトンを縮合させてビスフェノールＡを製造するに当
たり、上記スルホン酸型イオン交換樹脂として、スルホ
ン酸型イオン交換樹脂を、その水膨潤容積の５〜２０倍
容量のイオン交換水で洗浄したのち、該水膨潤容積の１
〜３倍容量のフェノール中にて５０〜８０℃の温度で２
〜５時間攪拌洗浄し、固液分離後の洗浄フェノール中の
硫黄濃度が１重量ｐｐｍ以下であるものを用いることを
特徴とするビスフェノールＡの製造方法。1. A method for producing bisphenol A by condensing phenol and acetone with a sulfonic acid type ion exchange resin as a catalyst and mercaptans as a cocatalyst, wherein the sulfonic acid type ion exchange resin is a sulfonic acid type ion exchange resin. After washing the exchange resin with ion exchange water having a volume of 5 to 20 times the water swelling volume, the water swelling volume of 1
2 to 3 volumes of phenol at a temperature of 50 to 80 ° C.
A method for producing bisphenol A, comprising washing with stirring for 5 to 5 hours and using a phenol having a sulfur concentration of 1 ppm by weight or less in the washed phenol after solid-liquid separation.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001064671A JP2002265403A (en) | 2001-03-08 | 2001-03-08 | Method for producing bisphenol a |
| PCT/JP2002/001924 WO2002072516A1 (en) | 2001-03-08 | 2002-03-01 | Method for producing bisphenol a |
| TW91104296A TWI310376B (en) | 2001-03-08 | 2002-03-07 | Process for producing bisphenol a |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001064671A JP2002265403A (en) | 2001-03-08 | 2001-03-08 | Method for producing bisphenol a |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002265403A true JP2002265403A (en) | 2002-09-18 |
Family
ID=18923457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001064671A Pending JP2002265403A (en) | 2001-03-08 | 2001-03-08 | Method for producing bisphenol a |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2002265403A (en) |
| TW (1) | TWI310376B (en) |
| WO (1) | WO2002072516A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007046474A1 (en) * | 2005-10-21 | 2007-04-26 | Idemitsu Kosan Co., Ltd. | Process for production of bisphenol a and method for judgment of ion-exchange resin |
| WO2019156391A1 (en) * | 2018-02-09 | 2019-08-15 | 주식회사 엘지화학 | Method for washing ion exchange resin and method for preparing bisphenol a |
| US20200115526A1 (en) * | 2017-06-16 | 2020-04-16 | Sabic Global Technologies B.V. | Use of sulfonic acid as stabilizer in polycarbonate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3190544B2 (en) * | 1995-06-30 | 2001-07-23 | 千代田化工建設株式会社 | Method for filling catalyst for bisphenol A production into reactor and method for producing high quality bisphenol A |
| JPH09176069A (en) * | 1995-12-26 | 1997-07-08 | Nippon Steel Chem Co Ltd | Production of bisphenols |
| JP2000143565A (en) * | 1998-11-12 | 2000-05-23 | Idemitsu Petrochem Co Ltd | Pretreatment of catalyst for producing bisphenol a and production of bisphenol a having stable hue |
-
2001
- 2001-03-08 JP JP2001064671A patent/JP2002265403A/en active Pending
-
2002
- 2002-03-01 WO PCT/JP2002/001924 patent/WO2002072516A1/en active Application Filing
- 2002-03-07 TW TW91104296A patent/TWI310376B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007046474A1 (en) * | 2005-10-21 | 2007-04-26 | Idemitsu Kosan Co., Ltd. | Process for production of bisphenol a and method for judgment of ion-exchange resin |
| US20200115526A1 (en) * | 2017-06-16 | 2020-04-16 | Sabic Global Technologies B.V. | Use of sulfonic acid as stabilizer in polycarbonate |
| US11692076B2 (en) * | 2017-06-16 | 2023-07-04 | Sabic Global Technologies B.V. | Interfacial polymerization process for polycarbonate in injection molding manufacturing with use of sulfonic acid as a stabilizer |
| WO2019156391A1 (en) * | 2018-02-09 | 2019-08-15 | 주식회사 엘지화학 | Method for washing ion exchange resin and method for preparing bisphenol a |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002072516A1 (en) | 2002-09-19 |
| TWI310376B (en) | 2009-06-01 |
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