1324145 玖、發明說明 【發明所屬之技術領域】 本發明係有關製造雙酚A[2，2 —雙（4 -羥苯基）丙 烷]中回收苯酚之方法’更詳細者係有關於雙酚A之工業上 製造步·驟中’由洗淨強酸性離子交換樹脂後之苯酚溶液進 行回收對於雙酚A品質無不良影響之可再利用之苯酚的方 法者。又’有關將回收之苯酚重覆進行再利用之苯酚的回 收方法者。 【先前技術】 公知者雙酚A乃做爲聚碳酸酯樹脂、聚丙烯酸酯樹脂 等之工程塑料、或環氧樹脂等原料之重要化合物者，近來 其需求曰益擴增中。 此雙酚A之製造時，以含硫胺化合物部份改性之強酸 性離子交換樹脂做爲觸媒使用之，做爲使用此觸媒之雙酚 A製造例者被揭示者如：藉由吡啶鏈烷硫醇於部份改性磺 酸系陽離子交換樹脂之存在下進行苯酚類與酮之縮合方法 者、理想之改性率爲2〜20%者（如：特開昭5 7 - 3 5 5 3 3號 公報）。又，被揭示使用吡啶鏈烷硫醇類做爲含硫胺化合 物者，至少於2個反應帶域進行分割丙酮後，製造選擇率 良好之雙酚A之方法者，改性率爲2〜40%，較佳者爲 3-3 0%者亦被揭示之（如：特開平11-246458號公報）。 於含硫胺化合物由部份改性之強酸性離子交換樹脂流 出含硫或氮之不純物後，製品之品質變差，因此，使含硫 -5- 1324145 胺化合物下部份改性之強酸性離子交換樹脂以苯酚進行洗 淨後開始進行反應，惟，洗淨時回收所使用苯酚之方法截 至目前尙未被提出》 【發明內容】 本發明鑑於上述問題，以提供一種由洗淨強酸性離子 交換樹脂後之苯酚溶液對於雙酚A品質無不良影響者，進 鲁行回收可再利用苯酚之方法，及重覆回收再利用所回收苯 酚之苯酚的回收方法爲目的者。 本發明者爲解決該課題，進行精密硏討後結果發現， 於製造雙酚A中，將含硫胺化合物下部份改性之強酸性離 子交換樹脂以苯酚洗淨後取得之苯酚溶液藉由蒸餾處理後 ，可完成該目的。基於此發現，進而完成本發明。 亦即，本發明係提供一種將含硫胺化合物下部份改性 之強酸性離子交換樹脂以苯酚洗淨後做爲觸媒，於該觸媒 # 之存在下進行苯酚與丙酮之縮合反應後，該反應生成液藉 由減壓蒸餾後分離成塔頂餾份與含雙酚A之塔底餾份，濃 縮該塔底餾份之液體經晶析後，由該晶析物回收雙酚A之 雙酚A的製造中，將該洗淨後之苯酚溶液進行蒸餾處理後 回收苯酚者爲其特徵之苯酚回收方法者。 本發明又提供一種使用該回收之苯酚做爲該縮合反應 之原料或該晶析時之結晶洗淨液者，重覆回收苯酚之方法 者。 1324145 【實施方式】 [發明實施之最佳形態] 本發明中做爲含硫胺化合物下部份改性之強酸性離子 交換樹脂之含硫胺化合物者如：3 -氫硫胺基吡啶等之氫硫 胺基吡啶類、2 —氫硫乙基胺等氫硫烷胺類、2, 2—二甲基 噻唑烷等之噻唑類、4 -胺基硫酚等胺基硫酚類、4 -吡啶乙 烷硫醇等之吡啶鏈烷硫醇等例。其中又以4 一吡啶乙烷硫醇 、2’ 2 —二甲基唾唑烷以及2 —氫硫乙基胺爲較佳者。 做爲強酸性離子交換樹脂例者如：磺化苯乙烯-二乙 烯苯共聚物、磺化交聯苯乙烯聚合物、苯酚甲醛一磺酸樹 脂、苯甲醛-磺酸樹脂等之磺酸型離子交換樹脂等例。 使用該含硫胺化合物後，使強酸性離子交換樹脂進行 部份改性之方法者並未特別限定，可使用先行公知之方法 者。如：適當之溶媒，較佳者爲水等之水性溶媒中，可將 強酸性離子交換樹脂與含硫胺化合物藉由反應成所期待改 性率後，可進行改性者。反應亦可於常溫下進行之，必要時 亦可進行加溫。藉由此反應使離子交換基（磺酸型離子交換 樹脂中爲磺酸基）與含硫胺化合物中之胺基進行反應後， 於部份離子交換基中導入含硫基後進行改性之。 其中，強酸性離子交換樹脂之「改性率」係指藉由強 酸性離子交換樹脂之含強酸性離子交換基之硫胺化合物之 莫耳改性率之意者。本發明中藉由含硫胺化合物之強酸性 離子交換樹脂改性率以5〜50%者宜，8~35%爲更佳者。當此 改性率不足5%或超出50%時，將恐降低雙酚A之收率。 -7- 1324145 本發明回收苯酚之方法中，以含硫胺化合物部份改性 之強酸性離子交換樹脂（以下，亦僅稱離子交換樹脂。）於 反應開始前以苯酚洗淨之。洗淨方法以連續式或分批式進 行之，洗淨後苯酚溶液中氮濃度至0.01〜5質量ppm進行者宜 。當洗淨後苯酚溶液中氮濃度太高則易使雙酚A之品質變差 。反之，使用使氮濃度過低之多量苯酚時，洗淨時間增加， 且，不利經濟面。 φ 以連續式進行洗淨時，LHSV (液空間速度）通常爲 0.02〜10hr_1，較佳者爲 0.05 〜5 hr-1。當 LHSV 不足 0.02 hr~ 1則恐拉長時間而效率變差，反之超出10hr_ 1則，務必 使用大量苯酚。洗淨溫度以45-110 °C者宜，更佳者爲 5 5~8 5 °C。當洗淨溫度太高則將加速離子交換樹脂之分解 ，反之，洗淨溫度太低則恐使苯酚固化之。 本發明製造雙酚A中，以上述之苯酚進行洗淨，以含 硫胺化合物下部份改性之強酸性離子交換樹脂做爲觸媒使 •用之，於此觸媒之存在下，將苯酚與丙酮於反應塔內進行 縮合反應後，取得反應生成液。反應方法並未特別限定， 一般以固定床連續反應、分批反應者宜。固定床連續反應 時該原料混合物之LHSV (液空間速度）通常爲〇.2~30 _ hr—1者宜，較佳者爲0.5〜SOhr-1。反應溫度爲50~100°C者 宜，較佳者爲60〜90 °C，苯酚/丙酮之比爲4〜30 (莫耳比） 者宜，較佳者爲6~20 (莫耳比）。 該縮合反應取得之反應生成液藉由減壓蒸餾後，由反 應塔之塔頂取得去除未反應丙酮、副產之水及部份苯酚之 -8 - 1324145 塔頂餾份。反應生成液之減壓蒸餾條件以壓力爲 6.7〜80.0kPa ，溫度爲7 0〜1 8 0 °C者宜。 含雙酚A與苯酚之該塔底餾份係將此藉由濃縮後做成 提高雙酚A濃度之濃縮液，由此濃縮液將雙酚A進行晶析 °塔底餾份之濃縮可藉由蒸餾後餾去過剩苯酚後進行之， 雙酚A濃度以濃縮至20~50質量％者宜。當此濃度低於20質 量％則將降低雙酚A之回收率，反之，此濃度超出50質量％ 則晶析後之生料之移送不易。晶析係使該濃縮液藉由冷卻 φ 至40〜70 °C後進行者。藉由晶析後取得做成結晶之雙酚A 與苯酚之加成物，藉由過濾或離子過濾等方法由該濃縮液 分離此加成物。 將分離之雙酚A與苯酚之加成物於100~2 00°C下進行 加熱熔融後，藉由減壓蒸餾由此加成物去除苯酚。蒸餾方 法係於壓力1.3~13.3kPa，溫度150〜190°C下進行者宜。又 ，亦可藉由蒸氣常壓蒸餾由雙酚A與苯酚之加成物去除苯 酣。 φ 去除苯酚之熔融狀態雙酚A係藉由一般造粒裝置進行 液滴，冷卻固化後做成製品。 反應開始時，於含硫胺化合物下部份改性之強酸性離 子交換樹脂以苯酚進行洗淨後取得之苯酚溶液藉由減壓蒸 _ 餾後，可回收苯酚。減壓蒸餾條件的壓力5.3〜66.7kP a， 溫度100〜l7〇°C者宜，壓力7〜5〇kPa，溫度12〇〜l5〇°C爲更 佳者。 此減壓蒸餾，可使用1根蒸餾塔後，變更條件後，分 -9- 1324145 開各成份者，亦可使用數根蒸餾塔進行分開各成份者。苯 酚溶液之蒸餾係使該反應生成液藉由減壓蒸餾取得塔頂餾 份同時進行蒸餾之，而以對蒸餾塔有效利用面爲宜者。 洗淨後之苯酚溶液的蒸餾與該塔頂餾份同時進行時， 此苯酚溶液與塔頂餾份相互之混合可以連續性進行之，亦 可以非連續性進行，洗淨後之苯酚溶液與塔頂餾份相互之 混合比並未特別限定。又，苯酚溶液與塔頂餾份相互之混 鲁合物進行蒸餾處理前係將此混合物加熱至40~80°C，更佳 者爲50~70°C後，去除丙酮者，而以丙酮之回收及有效利 用面爲宜。 由洗淨後之苯酚溶液或此苯酚溶液與塔頂餾份相互之 混合物所回收之苯酚以藉由蒸餾去除水份、或藉由蒸餾進 行精製者宜。此之操作後，亦可更藉由離子交換樹脂進行 精製之。此時，做爲離子交換樹脂者可使用酸型離子交換 樹脂者。 β 所回收之苯酚可做爲苯酚之與丙酮相互縮合反應原料 之使用者。又，可做爲晶析時呈結晶所取得苯酚Α與苯酚 相互之加成物洗淨液之使用者。 [實施例] 以下，藉由實施例進行本發明更詳細之說明’惟’本 發明並未受限於此等例者。 於內徑13mm，高度90 Omm之塡充層式反應器中進行 塡充74ml以水膨潤之4 -吡啶乙烷硫醇進行1 7%改性之強 -10- 1324145 酸性離子交換樹脂。此離子交換樹脂保持溫度於60°C之同 時以300ml之水進行洗淨後，以300ml苯酚洗淨，洗淨後之 苯酚溶液回收於燒瓶中。此苯酚溶液中含有11質量％之水 ，3.5質量ppm之硫份，0.8質量ppm之氮份。將此苯酚溶液 於常壓下進行加熱後去除水份。 再於1 70°C，減壓（66kPa )下回收苯酚溶液中之苯酚 。所回收之苯酚中含1 000質量ppm之水份，而完全未含有 硫份及氮份。 由該塡充層式反應器之入口於苯酚/丙酮比14 (莫耳 比），液空間速度6h — 1之條件下，8 0 °C下進行反應。丙酮 之轉化率爲9 5 %。 170 °C，減壓下，由反應生成液餾去未反應之丙酮， 生成水及部份苯酚後，進行分離塔頂餾份與塔底餾份。將 塔底餾份於154 °C下藉由減壓蒸餾後，餾去過剩之苯酚， 使雙酚A濃度做成40質量％，此濃度於43 °C下進行冷卻後 ，晶析後取得雙酚A與苯酚之加成物。雙酚A之色相評定 係於空氣氣氛下，260 °C，放置分鐘後之色相判定者。 色相之判定係利用ΑΡΗA標準液’以目測進行之。色相爲 10(APHA)者。 [實施例2] 實施例1中除使用由洗淨後之苯酚溶液所回收之苯酚與 丙酮做爲反應原料之外，與實施例1同法製造雙酚A。所取 得雙酚A之色相爲10 ( APHA)者。 -11 - 1324145 [實施例3] 實施例1中取得之塔頂餾份與實施例1中洗淨後之苯酸 溶液以質量比1: 1進行混合後，常壓下加熱至110 °c後， 由此混合物去除丙酮及水份。再於170 °c，減壓下回收苯 酚後，藉由磺酸型陽離子交換樹脂進行精製之。以精製之 苯酚與丙酮做爲反應原料使用之外，與實施例1同法製造 φ雙酚A。所取得雙酚A之色相爲10 ( APHA)者。 [比較例1] 實施例1中由洗淨後之苯酚溶液僅去除水份之苯酣與 丙酮做爲反應原料使用之外，與實施例1同法製造雙酚A。 取得雙酚A之色相爲25 ( APHA )者。 [比較例2 ] 實施例1中反應生成液與實施例1中洗淨後之苯酌溶液 以質量比1: 1進行混合後，170 °C，減壓下餾去未反應之 丙酮，水份及部份苯酚，進行分離塔頂餾份與塔底飽份。 將此塔底餾份與實施例1同法處理後，製造雙酚A。所取得 雙酚A之色相爲35(APHA)者。 [實施例4] 於內徑1 3mm、高度900mm之塡充層式反應器中，塡 入74ml之以2，2 -二甲基噻唑烷進行23 %改性之強酸性離 -12- 1324145 子交換樹脂。此離子交換樹脂保持溫度60 °C之同時以 300ml之水進行洗淨後，以300ml苯酚洗淨，將洗淨後之苯 酚溶液，回收於燒瓶中。此苯酚溶液中含有11質量％之水 份，3.6質量ppm之硫份，0.7質量ppm之氮份。將此苯酚溶 液於常壓下進行加熱後去除水份。 再於170 °C，減壓（66 kPa)下進行回收苯酚溶液中之 苯酚。所回收苯酚中含有1〇〇〇質量ppm之水，0.2質量ppm 之硫份 '及〇·1質量PPm之氮份。 由該塡充層式反應器之入口，於苯酚/丙酮比10 (莫 耳比）、液空間速度61T 1之條件，8〇t下進行反應之。丙 酮之轉化率爲65 %者。再與實施例1同法處理反應生成液後 ，製造雙酚A。所取得雙酚A之色相爲10 (APHA)者。 [實施例5] 實施例4中由洗淨後之苯酚溶液所回收之苯酚與丙酮做 爲反應原料使用之外，與實施例4同法製造雙酚A。所取得 雙酚A之色相爲10 ( APHA)者。 [實施例6] 實施例4中取得之塔頂餾份與實施例4中洗淨後之苯酚 溶液以質量比1: 1進行混合後，常壓下加熱至110 °C後， 由此混合物去除丙酮及水份。再於17(TC，減壓下進行回 收苯酚，藉由磺酸型陽離子交換樹脂進行精製之。精製之 苯酚與丙酮做爲反應原料使用之外，與實施例1同法製造 -13- 1324145 雙酚A。所取得雙酚A之色相爲10 (APHA)者。 [比較例3] 實施例4中由洗淨後之苯酚溶液僅去除水份之苯酚與 丙酮做爲反應原料使用之外，與實施例4同法製造雙酚A。 所取得雙酚A之色相爲25 ( APHA )者。 [比較例4 ] 實施例4中之反應生成液與實施例4中洗淨後之苯酚溶 液以質量比1 : 1進行混合後，於1 70 °C，減壓下餾去未反 應之丙酮，水份及部份苯酚後，進行分離塔頂餾份與塔底 餾份。將此塔底餾份與實施例4同法處理後，製造雙酚A。 所取得雙酚A之色相爲35 ( APHA)者。 [產業上可利用性] 藉由本發明後，於雙酚A工業上製造步驟中，由洗淨 強酸性離子交換樹脂之苯酚溶液可回收對於雙酚A品質無 不良影響之苯酚者。 -14-1324145 发明, DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a method for producing phenol recovered from bisphenol A [2,2-bis(4-hydroxyphenyl)propane], and more specifically relates to bisphenol A In the industrial manufacturing step, the method of recovering phenol which has no adverse effect on the quality of bisphenol A by recovering the phenol solution after the strong acidic ion exchange resin is recovered. Further, the method for recovering phenol which is used to recycle the recovered phenol is reused. [Prior Art] The bisphenol A is known as an engineering plastic such as a polycarbonate resin or a polyacrylate resin, or an important compound of a raw material such as an epoxy resin, and has recently been in demand for expansion. In the manufacture of the bisphenol A, a strongly acidic ion exchange resin partially modified with a thiamine compound is used as a catalyst, and a manufacturer of bisphenol A using the catalyst is disclosed as follows: A method in which a pyridine alkane thiol is condensed with a phenol and a ketone in the presence of a partially modified sulfonic acid-based cation exchange resin, and an ideal modification ratio is 2 to 20% (for example, JP-A-5-7-3) 5 5 3 Bulletin 3). Further, it has been disclosed that when a pyridine group-containing thiol compound is used as a thiamine-containing compound, a method of dividing acetone in at least two reaction zones is carried out, and a method of producing bisphenol A having a good selectivity is disclosed, and the modification ratio is 2 to 40. %, preferably 3-3 0% is also disclosed (for example, Japanese Laid-Open Patent Publication No. Hei 11-246458). After the sulfur-containing amine compound is eluted from the partially modified strong acidic ion exchange resin, the quality of the product is deteriorated, so that the strong acidity of the sulfur-containing 5-1324145 amine compound is partially modified. The ion exchange resin is washed with phenol, and the reaction is started. However, the method of recovering the phenol used at the time of washing has not been proposed until now. [Invention] The present invention has been made in view of the above problems to provide a strong acid ion by washing. The phenol solution after the exchange of the resin has no adverse effect on the quality of the bisphenol A, and the method of recovering the phenol by recycling the phenol, and the method of recovering and recycling the phenol recovered by the phenol is repeated. In order to solve this problem, the present inventors have found that in the production of bisphenol A, a phenol solution obtained by washing a strongly acidic ion exchange resin partially modified with a thiamine compound with phenol is used. This can be done after the distillation treatment. Based on this finding, the present invention has been completed. That is, the present invention provides a strong acidic ion exchange resin partially modified with a thiamine compound, which is washed with phenol and used as a catalyst. After the condensation reaction of phenol and acetone in the presence of the catalyst # The reaction product is separated into an overhead fraction and a bottom fraction containing bisphenol A by distillation under reduced pressure, and the liquid of the bottom fraction is concentrated by crystallization, and bisphenol A is recovered from the crystallization. In the production of bisphenol A, the phenol recovery method is characterized in that the washed phenol solution is subjected to distillation treatment to recover phenol. Further, the present invention provides a method of repeatedly recovering phenol by using the recovered phenol as a raw material of the condensation reaction or a crystallization cleaning liquid at the time of crystallization. [Embodiment] [Best Mode for Carrying Out the Invention] In the present invention, a thiamine-containing compound which is a partially modified strong acidic ion exchange resin containing a thiamine compound is, for example, a 3-hydrothiazylpyridine or the like. Hydrothiazolidines such as hydrothiazolidine and 2-hydrothioethylamine; thiazoles such as 2,2-dimethylthiazolidine; and aminothiophenols such as 4-aminothiophenol; Examples of the pyridine alkanethiol such as pyridinium ethanethiol. Among them, 4-pyridylethanethiol, 2'-2-dimethylsoxazolidine and 2-hydrothioethylamine are preferred. As a strong acid ion exchange resin, such as: sulfonated styrene-divinylbenzene copolymer, sulfonated crosslinked styrene polymer, phenol formaldehyde monosulfonic acid resin, benzaldehyde-sulfonic acid resin, etc. Exchange resin and the like. The method of partially modifying the strongly acidic ion exchange resin after the use of the thiamine-containing compound is not particularly limited, and a known method can be used. For example, in a suitable solvent, preferably an aqueous solvent such as water, the strongly acidic ion exchange resin and the thiamine-containing compound can be modified by reacting to a desired degree of modification. The reaction can also be carried out at room temperature, and if necessary, heating can also be carried out. By reacting the ion exchange group (sulfonic acid group in the sulfonic acid type ion exchange resin) with the amine group in the thiamine-containing compound by this reaction, after introducing a sulfur-containing group into a part of the ion exchange group, the modification is carried out. . Here, the "modification rate" of the strongly acidic ion exchange resin means the molar modification ratio of the thiamine compound having a strongly acidic ion exchange group by a strongly acidic ion exchange resin. In the present invention, the modification rate of the strongly acidic ion exchange resin containing a thiamine compound is preferably 5 to 50%, and more preferably 8 to 35%. When the modification ratio is less than 5% or exceeds 50%, the yield of bisphenol A is feared to be lowered. -7- 1324145 In the method for recovering phenol of the present invention, a strongly acidic ion exchange resin partially modified with a thiamine-containing compound (hereinafter also referred to as an ion exchange resin) is washed with phenol before the start of the reaction. The washing method is carried out in a continuous or batchwise manner, and the nitrogen concentration in the phenol solution after washing is preferably 0.01 to 5 ppm by mass. When the nitrogen concentration in the phenol solution is too high after washing, the quality of bisphenol A is deteriorated. On the other hand, when a large amount of phenol having a too low nitrogen concentration is used, the washing time is increased and the economical surface is unfavorable. When φ is washed continuously, the LHSV (liquid space velocity) is usually 0.02 to 10 hr_1, preferably 0.05 to 5 hr-1. When the LHSV is less than 0.02 hr~1, it will be delayed for a long time and the efficiency will be worse. Otherwise, if it exceeds 10hr_1, it is necessary to use a large amount of phenol. The washing temperature should be 45-110 °C, and the better is 5 5~85 °C. When the washing temperature is too high, the decomposition of the ion exchange resin will be accelerated. On the contrary, if the washing temperature is too low, the phenol may be solidified. The bisphenol A produced by the invention is washed with the above phenol, and is used as a catalyst by using a partially acidic modified ion exchange resin containing a thiamine compound, and in the presence of the catalyst, After the condensation reaction of phenol and acetone in the reaction column, a reaction product liquid is obtained. The reaction method is not particularly limited, and it is generally preferred to carry out a continuous reaction in a fixed bed or a batch reaction. The LHSV (liquid space velocity) of the raw material mixture in the continuous reaction of the fixed bed is usually 〇. 2~30 hr hr-1, preferably 0.5~SOhr-1. The reaction temperature is preferably from 50 to 100 ° C, preferably from 60 to 90 ° C, and the ratio of phenol to acetone is from 4 to 30 (mole ratio), preferably from 6 to 20 (mole ratio). . The reaction product obtained by the condensation reaction is subjected to distillation under reduced pressure, and an -8 - 1324145 overhead fraction from which unreacted acetone, by-produced water, and a part of phenol are removed is obtained from the top of the reaction column. The vacuum distillation conditions of the reaction product are preferably 6.7 to 80.0 kPa and the temperature is 70 to 180 °C. The bottoms fraction containing bisphenol A and phenol is concentrated to obtain a concentrate for increasing the concentration of bisphenol A, whereby the concentrate is subjected to crystallization of bisphenol A. After the excess phenol is distilled off by distillation, the concentration of bisphenol A is preferably 20 to 50% by mass. When the concentration is less than 20% by mass, the recovery of bisphenol A is lowered. Conversely, if the concentration exceeds 50% by mass, the transfer of the raw material after crystallization is not easy. The crystallization system is carried out by cooling φ to 40 to 70 °C. The crystallized adduct of bisphenol A and phenol is obtained by crystallization, and the adduct is separated from the concentrate by filtration or ion filtration. The adduct of the separated bisphenol A and phenol is heated and melted at 100 to 200 ° C, and then the acetate is removed by distillation under reduced pressure. The distillation method is carried out at a pressure of 1.3 to 13.3 kPa and a temperature of 150 to 190 ° C. Further, benzoquinone may be removed from the adduct of bisphenol A and phenol by vapor atmospheric distillation. φ Removal of molten state of phenol Bisphenol A is formed into droplets by a general granulator, cooled and solidified to form a product. At the beginning of the reaction, the phenol solution obtained by washing the strongly acidic ion exchange resin partially modified with the thiamine compound with phenol is distilled off under reduced pressure to recover phenol. The pressure under vacuum distillation conditions is 5.3 to 66.7 kP a, the temperature is 100 to 17 〇 °C, the pressure is 7 to 5 kPa, and the temperature is 12 〇 to 15 〇 °C. In this vacuum distillation, one distillation column can be used, and after changing the conditions, the components can be separated by -9- 1324145, or a plurality of distillation columns can be used to separate the components. The distillation of the phenol solution is carried out by subjecting the reaction product to distillation and distillation to obtain an overhead fraction, and it is preferred to use the surface effectively for the distillation column. When the distillation of the washed phenol solution is carried out simultaneously with the overhead fraction, the mixing of the phenol solution and the overhead fraction may be carried out continuously, or may be discontinuous, and the washed phenol solution and the tower may be carried out. The mixing ratio of the top fractions to each other is not particularly limited. Further, before the distillation treatment of the mixed solution of the phenol solution and the overhead fraction, the mixture is heated to 40 to 80 ° C, more preferably 50 to 70 ° C, and the acetone is removed, and acetone is used. It is advisable to recycle and effectively use the surface. The phenol recovered from the washed phenol solution or the mixture of the phenol solution and the overhead fraction is preferably removed by distillation to remove water or by distillation. After this operation, it can be further refined by an ion exchange resin. At this time, as the ion exchange resin, an acid type ion exchange resin can be used. The phenol recovered by β can be used as a raw material for the mutual condensation reaction of phenol and acetone. Further, it can be used as a user for obtaining an adduct cleaning solution of phenolphthalein and phenol which is crystallized during crystallization. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited thereto. In a ruthenium-filled reactor having an inner diameter of 13 mm and a height of 90 mm, 74 ml of water-swelled 4-pyridine thiol was subjected to a 7% modification of strong -10- 1324145 acidic ion exchange resin. This ion exchange resin was washed with 300 ml of water while maintaining the temperature at 60 ° C, and then washed with 300 ml of phenol, and the washed phenol solution was recovered in the flask. This phenol solution contained 11% by mass of water, 3.5 ppm by mass of sulfur, and 0.8 ppm by mass of nitrogen. The phenol solution is heated under normal pressure to remove water. The phenol in the phenol solution was recovered under reduced pressure (66 kPa) at 1 70 °C. The recovered phenol contains 1 000 ppm by mass of water, and does not contain sulfur and nitrogen at all. The reaction was carried out at 80 ° C from the inlet of the packed-layer reactor at a phenol/acetone ratio of 14 (mol ratio) at a liquid space velocity of 6 h -1 . The conversion of acetone was 95%. At 170 ° C, unreacted acetone was distilled off from the reaction product under reduced pressure to form water and a part of phenol, and then the top fraction and the bottom fraction were separated. The bottom fraction was distilled under reduced pressure at 154 ° C, and excess phenol was distilled off to adjust the concentration of bisphenol A to 40% by mass. After the concentration was cooled at 43 ° C, crystallization was carried out to obtain a double An adduct of phenol A and phenol. The hue evaluation of bisphenol A was carried out under an air atmosphere at 260 ° C, and the hue was judged after being left for a minute. The determination of the hue was carried out by visual inspection using ΑΡΗA standard solution ‘. The hue is 10 (APHA). [Example 2] In Example 1, bisphenol A was produced in the same manner as in Example 1 except that phenol and acetone recovered from the washed phenol solution were used as a reaction raw material. The bisphenol A was obtained in a hue of 10 (APHA). -11 - 1324145 [Example 3] The top fraction obtained in Example 1 and the washed benzoic acid solution in Example 1 were mixed at a mass ratio of 1:1, and then heated to 110 ° C under normal pressure. , the mixture removes acetone and water. Further, after recovering phenol at 170 ° C under reduced pressure, it was purified by a sulfonic acid type cation exchange resin. φ bisphenol A was produced in the same manner as in Example 1 except that purified phenol and acetone were used as the reaction materials. The obtained bisphenol A has a hue of 10 (APHA). [Comparative Example 1] In Example 1, bisphenol A was produced in the same manner as in Example 1 except that phenylhydrazine having only water removed from the washed phenol solution and acetone were used as a reaction raw material. Obtain a bisphenol A hue of 25 (APHA). [Comparative Example 2] The reaction product in Example 1 and the benzene solution after washing in Example 1 were mixed at a mass ratio of 1:1, and then unreacted acetone and water were distilled off at 170 ° C under reduced pressure. And part of the phenol, the separation overhead fraction and the bottom of the bottom are saturated. This bottom fraction was treated in the same manner as in Example 1 to produce bisphenol A. The obtained bisphenol A had a hue of 35 (APHA). [Example 4] In a ruthenium-filled reactor having an inner diameter of 1 3 mm and a height of 900 mm, 74 ml of 2,2-dimethylthiazolidine was used for 23% modification of strong acidity from -12 to 1324145. Exchange resin. This ion exchange resin was washed with 300 ml of water while maintaining the temperature at 60 ° C, and then washed with 300 ml of phenol, and the washed phenol solution was recovered in a flask. This phenol solution contained 11% by mass of water, 3.6 ppm by mass of sulfur, and 0.7 ppm by mass of nitrogen. The phenol solution is heated under normal pressure to remove water. The phenol in the phenol solution was recovered at 170 ° C under reduced pressure (66 kPa). The recovered phenol contains 1 〇〇〇 mass ppm of water, 0.2 ppm by mass of sulfur 'and 〇·1 by mass of PPm of nitrogen. From the inlet of the packed-layer reactor, the reaction was carried out under the conditions of a phenol/acetone ratio of 10 (mol ratio) and a liquid space velocity of 61 T 1 at 8 Torr. The conversion rate of acetone was 65%. Further, after the reaction product was treated in the same manner as in Example 1, bisphenol A was produced. The obtained bisphenol A has a hue of 10 (APHA). [Example 5] In Example 4, bisphenol A was produced in the same manner as in Example 4 except that phenol and acetone recovered from the washed phenol solution were used as a reaction raw material. The obtained bisphenol A has a hue of 10 (APHA). [Example 6] The tar solution obtained in Example 4 and the phenol solution after washing in Example 4 were mixed at a mass ratio of 1:1, and then heated to 110 ° C under normal pressure, thereby removing the mixture. Acetone and water. Further, 17 (TC, phenol was recovered under reduced pressure, and purified by a sulfonic acid type cation exchange resin. The purified phenol and acetone were used as a reaction raw material, and the same method as in Example 1 was used to manufacture -13 - 1324145 Phenol A. The hue of the obtained bisphenol A was 10 (APHA). [Comparative Example 3] In Example 4, phenol and acetone which only remove water from the washed phenol solution were used as a reaction raw material, and The bisphenol A was produced in the same manner as in Example 4. The color of the obtained bisphenol A was 25 (APHA). [Comparative Example 4] The reaction product in Example 4 and the phenol solution after washing in Example 4 were mass-produced. After mixing at a ratio of 1:1, the unreacted acetone, water and a portion of the phenol are distilled off under reduced pressure at 1 70 ° C, and then the top fraction and the bottom fraction are separated. After the same treatment as in Example 4, bisphenol A was produced. The obtained bisphenol A had a hue of 35 (APHA). [Industrial Applicability] By the present invention, in the bisphenol A industrial manufacturing step, The phenol solution which cleans the strong acidic ion exchange resin can recover the phenol which has no adverse effect on the quality of bisphenol A. 14-