1310376 A7 __B7 五、發明説明（》 &MMM. (請先閱讀背面之注意事項再填寫本頁) 本發明有關一種製備雙酚A之方法，詳言之，有關一 種製備雙酚A { 2，2 -雙（4 一羥基苯基）丙烷丨之方 法，其係使用磺酸型離子交換樹脂作爲觸媒由酚與丙酮製 備者，其中選擇地施用能夠在短時間內被淸潔的觸媒。 i景技術 已知雙酚A係作爲環氧樹脂或工程塑膠（如聚碳酸酯 樹脂及聚芳撐樹脂）之起始原料的重要化合物，及因此它 的需要性有逐年地明顯擴增之傾向。 雙酚A係在酸性觸媒存在下及可在以硫化合物等作爲 共觸媒之情形下，藉由過量的酚與丙酮之縮合反應而製得 者。 迄今’已使用無機酸（如硫酸及氯化氫）作爲酸性觸 媒而用於反應中，然而，近年來著重於已被引進工業用途 方面之陽離子交換樹脂的應用（參閱英國專利 GB 842209 '849565 及 883391)。 經濟部智慧財產局員工消費合作社印製 另一方面’已知作爲共觸媒之適合的硫化合物包括具 有或未具有取代基之烷基硫醇化合物，如甲基硫醇 '乙基 硫醇及硫代二元醇酸（參閱美國專利2 3 5 9 2 4 2及 2775620)，該硫醇具有提高反應速率及同時提高 選擇性之功能，例如在雙酚A之製法中，形成的反應副產 物2 -（2 -羥基苯基）一 2 -（4 —羥基苯基）—丙烷 (o’p’ -異構物）爲主成分，及除其之外者爲參酹與 本紙張AA適用中關家標準（CNS ) Α4· ( 21GX297公釐) ΤΓ. ~ 1310376 A7 B7 五、發明説明（2 (請先閲讀背面之注意事項再填寫本頁) 多酚’特別是當使用雙酚A作爲聚碳酸酯樹脂或聚芳撐之 起始原料時’需要將上述副產物的含量最小化，及要求非 常純與不會著色，依此’可使用硫醇化合物以提高反應速 率、抑制副產物的形成及提高選擇性之方式達成。 在酚與丙酮進行縮合反應之工業製備雙酚A之例中， 一般採用連續式固定床反應系統，其中酚與丙酮作爲起始 原料及硫醇作爲共觸媒’其被連續地供給反應塔，該反應 塔塡有上述陽離子交換樹脂作爲觸媒。 在連續式固定床反應系統中，一般使用由至少二個反 應器構成的多階式固定床反應設備，該反應器爲串聯連接 及其各塡有前述陽離子交換樹脂作爲觸媒。而由催化活性 觀點來看，作爲陽離子交換樹脂者包括普遍被使用的強酸 性磺酸型離子交換樹脂。 經濟部智慧財產局員工消費合作杜印製 然而’已知當使用磺酸型離子交換樹脂作爲觸媒時， 從前述離子交換樹脂中的磺酸之移除作用係在縮合反應起 始後發生，及於隨後的步驟中流入反應液體之硫酸曝露在 高溫的情況下，該酸造成雙酚A之分解，因而形成有色的 不純物副產物’由於前述有色的不純物產生不利的情形如 雙酚A之色度的衰減作用，因此其需要大幅地減少有色的 不純物’以期能製造具有滿意色度且沒有著色的雙酚A, 尤其是相關於光碟、光纖等用的聚碳酸酯中作爲原料之雙 酚A情況中。 諸如此種情形，迄今已嘗試各種淸潔方祛以進行前述 磺酸型離子交換樹脂之預處理，例如，已揭露一種方法其 -5- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1310376 A7 __ B7 五、發明説明（3 (請先閲讀背面之注意事項再填寫本頁) 包含以去離子水淸潔離子交換樹脂直到該淸潔液體之比電 導（specific conductivity )於 2 5 °C 變成低於 5 0 # Ώ — 1 / c m爲止，及然後將該經淸潔的離子交換樹脂脫水（（ 參閱日本專利申請公開第1 7 3 8 5 8/1 9 9 7號（平 成9年））；一種方法其包含以水淸潔陽離子交換樹脂， 接著以酚淸潔該樹脂（（參閱日本專利申請公開第 176069/1997號（平成9年））：一種方法其 包含在反應器中堆塡磺酸型離子交換樹脂，然後以水淸潔 該樹脂直到淸潔廢水的p Η値變成6或以上爲止，及隨後 以酚淸潔該樹脂直到在淸潔的酚中除去的磺酸之濃度以重 量計變成2 p P m或以下爲止（（參閱日本專利申請公開 第143565/2000號（平成12年）），·及其他 類似方法。 經濟部智慧財產局員工消費合作社印製 如上所述，熟知在酸型陽離子交換樹脂之中，以水及 /或酚淸洗係有效的，且在塡充觸媒後及在取代觸媒後的 產物色度可藉充分地進行淸潔而被維持，然而目前不利的 情況發生其在反應器塡充觸媒之後需花費極長的時間來進 行以水及酚之淸潔，因而顯著地損及經濟效益，例如，在 空氣中、濕潤狀態中已保存一段長時間的磺酸型離子交換 樹脂之例中，包含聚-苯乙烯磺酸之有色的洗出液涵蓋在 表面及內部之孔中’因此需花費較長時間來淸潔。 由前述觀之’需要簡單地了解樹脂的淸潔性能，亦即 ’在流動系統反應器塡充磺酸型離子交換樹脂之前以水及 酚淸潔之需要的預測時間。 -6 - 本紙張尺度逍用中國國家標準（CNS ) A4規格（210X297公釐） 1310376 A7 B7 五、發明説明（4 發明之掲露 在此情況下’本發明之通常目的係提供一種製備雙酚 A之方法，其係在磺酸型離子交換樹脂作爲觸媒存在下從 酚與丙酮製備者，其中藉簡易方法僅需在短時間內淸潔的 離子交換樹脂被挑選出而用於選擇的用途。 本發明之其它目的將由下文揭露的說明書內容變得更 顯著。 在此情況中，爲了達到上述目的，本發明人集聚了嚴 密的、大規模的硏究與調查，其結果已發現本發明目的可 藉使用特定的簡易淸潔方法進行磺酸型離子交換樹脂之清 潔處理，該方法係使用離子交換水及酚處理，最終獲得具 有淸潔的酚之硫含量爲至多1 p pm的磺酸型離子交換樹 脂，及使用該樹脂作爲觸媒用以形成雙酚。本發明係以前 述發現與資料作爲基礎而完成。 詳言之，本發明提供一種製備雙酚A之方法，其係在 磺酸型離子交換樹脂作爲觸媒及硫醇作爲共觸媒之存在下 ，進行酚與酮之縮合反應，其特徵在於使用磺酸型離子交 換樹脂其爲以體積5至2 0倍於樹脂的水膨潤體積的離子 交換水淸潔，然後以體積1至3倍於樹脂的水膨潤體積的 酚在5 0至8 0 °C溫度範圍下攪拌淸潔持續2至5小時， 及進行固-液分離作用，其中該用於淸潔之經分離的酚具 有硫含量以重量計爲至多一（1) ppm。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------·¥-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1310376 A7 _____ B7 五、發明説明（3 另可能地將任何的硫醇固定至上述磺酸型離子交換樹 脂上，及使其產生與作爲共觸媒之相同的效果。 (請先閲讀背面之注意事項再填寫本頁) 所使用的硫醇的含量一般選在〇 . 1至2 0莫耳之範 圍’較佳爲1至2 0莫耳，以作爲起始原料之丙酮爲基準 〇 欲用於本發明製備雙酚A之方法中的酚對丙酮之比例 不特別受限制，但從精製該最終雙酚A之容易性、經濟效 益等因素觀點來看，未反應的丙酮之含量較佳爲儘可能地 小，依此使用高過其化學計量的過量酚係有利的，因此每 一莫耳丙酮通常使用含量爲3至3 0莫耳的酚，較佳爲5 至1 5莫耳。在雙酚A之製法中，除了反應液體有不合乎 常理的高黏度情況或反應在類如低溫下進行經固化作用而 使操作困難的情況之外，通常是不需要反應溶劑。 經濟部智慧財產局員工消費合作社印製 於本發明中使用連續多階段式固定床反應系統，其中 酚、丙酮及前述硫醇被連續地供入反應塔中以進行反應， 該反應塔爲塡充有藉由進行前述簡易淸潔方法挑選出的磺 酸型離子交換樹脂，及其僅需在短時間內被淸潔，在根據 本發明之方法中，塡充於反應塔中的磺酸型離子交換樹脂 之淸潔處理首先在反應開始之前進行，最初步驟中，水通 過塡充有磺酸型離子交換樹脂之反應塔以進行以水之淸潔 處理直到廢棄的淸潔水之P H値到達約5 . 5至7爲止’ 之後，酚通過該反應塔’同時維持離子交換樹脂之溫度爲 5 0至8 0Τ：之範圍，其大致上以酚取代樹脂中的水，因 而繼續進行以酚淸潔的處理直到用於淸潔的酚之硫含量以 本紙張尺度適用中國國家標準（CNS ) Μ規格（210Χ 29*7公董） -11 - 1310376 A7 B7 五、發明説明（$ 重量計變爲1 P pm爲止。 {請先閱讀背面之注意事項再填寫本頁} 隨後，酚、丙酮及前述硫醇連續地供入反應塔中經由 連續固定床反應系統進行反應。 接著，將詳說明連續固定床反應系統的反應條件，首 先，丙酮/酚的莫耳比一般選在1/3 0至1/3之範圍 ，較佳爲1/1 5至1/5。當該莫耳比低於1/30時 ，恐有發生不合乎常理的低反應速率之虞，而當該莫耳比 例大於1 / 3時，則有造成過量不純物形成之傾向，及會 降低對雙酚A的選擇性。另一方面，當硫醇在陽離子交換 樹脂上不是固定時，硫醇/丙酮之莫耳比通常選在0 . 1 /1 0 0至2 0/1 00之範圍，較佳爲1/1 00至 1 0/1 00。當莫耳比低於0 _ 1/1 00時，恐有缺 乏在提高反應速率或對雙酚A之選擇率方面展現足夠的操 作效果能力之虞，而當莫耳比高於2 0/1 0 〇時，會造 成在提高反應速率或對雙酚A之選擇率方面的操作效果無 法在如此高量下被確認。 經濟部智慧財產局員工消費合作社印製 另外，反應溫度通常選在4 0至1 5 0 °C之範圍，較 佳爲60至1 1 0°C。當反應溫度低於40°C時，會產生 不合乎常理的低反應速率，及除此之外，會產生極高黏度 的反應液體，因而在此情況下恐有發生固化反應之虞，反 之，當反應溫度高於1 5 0 °c時，使得反應難以控制、對 雙酚A ( p，p ’ -異構物）之選擇性衰減及使作爲觸媒 之陽離子交換樹脂產生另外的分解或衰減作用。通常’ LHSV (液體每小時空間速度）選在〇 _ 2至3 0 本紙張尺度適用中國國家標準（CNS ) A4规格（21〇X297公釐) 「12 - 1310376 A7 B7 五、發明説明（釦 hr— 1之範圍，較佳爲0 . 5至10hr—、 (請先閲讀背面之注意事項再填寫本頁) 於根據本發明之方法中，由來自反應塔的反應混合物 可藉已熟知的方法進行後處理以收集標的產物雙酚A，以 下將以一個後處理實例說明之，首先，在結晶之前進行反 應混合物的濃縮反應，濃縮條件不特別受限制，惟通常包 括溫度爲1 3 0至1 7 〇°C之範圍及壓力爲1 3至5 3 k P a之範圍的條件。當溫度低於1 3 0 °C時，必要條件 爲高真空度，而當溫度高於1 7 0 °C時，則會造成不純物 含量的增加或產生反應產物的著色作用。將在經濃縮的殘 餘液體中的雙酚A濃度界定在2 5至4 0重量％係有利的 ，但當其濃度低於2 5重量％時，則會造成低的雙酚A回 收率，而當其濃度高於4 0重量％時，會造成在結晶後漿 液傳送困難。 經濟部智慧財產局員工消費合作社印製 來自經濃縮的殘餘液體之雙酚A與酚加成物的結晶作 用通常藉真空冷卻結晶方法進行，其步驟包含在減壓下利 用水蒸發作用的潛熱冷卻，在此前述方法中，結晶處理通 常在包括溫度爲4 0至7 0°C之範圍與壓力爲3至1 3 k P a之範圍的條件下，藉將約3至2 0重量％的水加入 經濃縮的殘餘液體中進行。而當欲添加的水低於3重量％ 時，會造成熱移除容量不足，而當水高於2 0重量％時， 會不適當地造成雙酚A的溶解流失量增加，更且，當結晶 溫度低於4 0 °C時，恐有造成結晶液體黏度增加或產生結 晶液體的固化反應之虞，而當結晶溫度高於7 0 °C時，會 不適當地造成雙酚A的溶解流失量增加。 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格.（210X297公釐） 1310376 A7 ___B7 五、發明説明（力1 (請先閲讀背面之注意事項再填寫本頁) 接著，經上述方式結晶的雙酚A與酚加成物其藉熟知 方法分離，及隨後以酚進行淸潔處理，然後在包括溫度通 常選在1 30至200 °C之範圍（較佳爲工50至1 80 °C )及壓力選在3至2 0 k P a之範圍的條件下，將已進 行淸潔處理的加成物分離成雙酚A與酚。 在藉由分離處理所獲得的雙酚A中的殘餘酚，其藉汽 提方法或類似方法實質上完全地被移除，依此可獲得高品 質的雙酚A。 下文中’本發明將以相關的實施例及比較例詳盡地說 明，然而其將不會限制本發明。 實例1 (1 )簡易的淸潔試驗 於1 0 0毫升（m L )樣品瓶中饋入具有水膨潤體積 爲5 OmL之磺酸型離子交換樹脂，之後倂入離子交換水 ’而使包括樹脂之全部體積爲1 〇 OmL，接著，同時攪 拌含水的樹脂，使其靜置，及抽取上層液體至樹脂的介面 經濟部智慧財產局員工消費合作社印製 。重複相同的步驟1 〇次，及所淸潔的樹脂在真空下過濾 以移除大部份的水。 樹脂再度回到上述容器中，倂入酚，而使包括樹脂之 全部體積爲1 0 OmL，攪拌，使其靜置，及抽取上層液 體’進行檢測其中的硫含量，結果以重量計爲低於1 Ppm。 本紙張尺度適用中.國國家橾準（CNS ) A4規格（210X297公釐） -14 - 1310376 A7 B7 五、發明説明（如 (2 )連續式流動試驗 於內徑1 4mm及長度4 5 〇mm的 反應器中塡入體積7 OmL的與前述步驟 酸型離子交換樹脂，隨後將離子交換水連 其流速爲1 0 m L /小時，持續2 5小時 淸潔的2 5小時後檢測廢棄的淸潔水之P 蕊試紙上顯示爲中性値5 . 5。 當酚之水含量以重量計爲0 . 3 %時 的溫度提升至7 0 t及使酚以流速1 〇 m 應器，持續2 5小時以將樹脂脫水，此時 APHA色度之檢測結果分別爲4 P Pm 隨後，在相同於前述脫水反應之條件下進f了利用酣之 淸潔處理，在從開始以酚淸潔的1 〇小時後’酣之硫含量 以重量計下降至低於1 P pm，及其APHA色度爲1 5 比較例1 經濟部智慧財產局員工消費合作社印製 不銹鋼管製成的 (1 )相同的磺 續地通過反應器 ，因此，從開始 Η値，結果在石 ，接著將樹脂床 L /小時通過反 酚的硫含量與其 ，與3 0或以上 (請先閲讀背面之注意事項再填寫本頁) (1 )簡易的淸潔試驗 將與用於實例1之相同的磺酸型離子父換樹脂保存於 空氣中2個月，之後重複實例1之步驟（1 ) ’收集上層 液體以檢測其硫含量’結果以重里5十爲4 p p 2 )連續式流動試驗 本紙張尺度適用中國國家標準（CNS M4規格（210X297公釐） 1310376 A7 -___^ & '發明説明（ 使用與前述步驟（1 )相同之已經在空氣中保存2個 月的磺酸型離子交換樹脂重複實例1 ( 2 )步驟。 (請先閲讀背面之注意事項再填寫本頁) 因此，從開始淸潔的2 5小時後檢測廢棄的淸潔水之 P Η値，結果在石蕊試紙顯示爲中性値5 . 〇。在以酸脫 水反應2 5小時後，酚之水含量爲0 . 3%時’此時酸的 硫含量與其A Ρ ΗΑ色度之檢測結果分別爲8 P pm ’與 3 0或以上。 隨後，在相同於前述脫水反應之條件下進行利用酸之 淸潔處理，在從開始以酚淸潔的4 0小時後，酚之硫含量 以重量計下降至低於1 p pm，及其APHA色度爲2 〇 由實例1及比較例1可了解，該簡易的淸潔試驗結果 與連續式流動試驗之確認結果之間的關係可被淸楚地確認 產業利用件 經濟部智慧財產局員工消費合作社印製 根據本發明，由酚與丙酮可有效地製備雙酚A ’其以 經濟有利的方式藉使用磺酸型離子交換樹脂作爲觸媒而製 備者，而由於特定簡易的淸潔方法，其僅需使用短時間進 行淸潔。 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐}1310376 A7 __B7 V. INSTRUCTIONS (" & MMM. (Please read the note on the back and then fill out this page) The present invention relates to a method for preparing bisphenol A, in particular, a preparation of bisphenol A { 2, A method of 2-bis(4-hydroxyphenyl)propane oxime which is prepared from phenol and acetone using a sulfonic acid type ion exchange resin as a catalyst, wherein a catalyst which can be cleaned in a short time is selectively applied. It is known that bisphenol A is an important compound for the starting material of epoxy resin or engineering plastics (such as polycarbonate resin and polyarylene resin), and therefore its demand has a tendency to be significantly expanded year by year. Bisphenol A is produced by the condensation reaction of excess phenol with acetone in the presence of an acidic catalyst and in the case of a sulfur compound or the like as a co-catalyst. So far, inorganic acids such as sulfuric acid have been used. And hydrogen chloride) is used as an acid catalyst in the reaction. However, in recent years, it has focused on the application of cation exchange resins that have been introduced into industrial applications (see British Patent GB 842209 '849565 and 883391). On the other hand, the sulphur compounds known as co-catalysts include alkyl thiol compounds with or without substituents, such as methyl mercaptan 'ethyl mercaptan and thiodi Alkyd (see U.S. Patent No. 2 3 5 9 2 2 2 and 2775620), which has the function of increasing the reaction rate and simultaneously improving the selectivity, for example, in the preparation of bisphenol A, the reaction by-product 2 - ( 2-hydroxyphenyl)-2-(4-hydroxyphenyl)-propane (o'p'-isomer) as the main component, and other than the reference standard for the application of AA and AA (CNS) Α4· (21GX297 mm) ΤΓ. ~ 1310376 A7 B7 V. Description of the invention (2 (please read the note on the back and then fill out this page) Polyphenols' especially when using bisphenol A as polycarbonate resin Or when starting the raw material of polyarylene, the content of the above-mentioned by-products needs to be minimized, and it is required to be very pure and not colored. Accordingly, a thiol compound can be used to increase the reaction rate, inhibit the formation of by-products, and improve the selection. The way of sexuality is achieved. The condensation reaction between phenol and acetone In the industrial preparation of bisphenol A, a continuous fixed bed reaction system is generally employed in which phenol and acetone are used as starting materials and thiol is used as a co-catalyst, which is continuously supplied to a reaction column having the above cations. Exchange resin as a catalyst. In a continuous fixed bed reaction system, a multi-stage fixed bed reaction apparatus consisting of at least two reactors is generally used, which is connected in series and each of which has the aforementioned cation exchange resin as a contact From the viewpoint of catalytic activity, as a cation exchange resin, it includes a strongly acidic sulfonic acid type ion exchange resin which is generally used. Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperation, dulu printing, however, 'known to use sulfonic acid type ions When the exchange resin is used as a catalyst, the removal of the sulfonic acid from the aforementioned ion exchange resin occurs after the initiation of the condensation reaction, and in the case where the sulfuric acid flowing into the reaction liquid is exposed to a high temperature in the subsequent step, the acid is caused. Decomposition of bisphenol A, thus forming a colored impurity by-product, due to the aforementioned adverse effects of colored impurities such as double The chromaticity of A, so it needs to greatly reduce the colored impurities' in order to produce bisphenol A with satisfactory chroma and no coloration, especially as a raw material in polycarbonates for optical discs, optical fibers, etc. In the case of bisphenol A. In such cases, various cleaning methods have been tried so far to carry out the pretreatment of the aforementioned sulfonic acid type ion exchange resin. For example, a method has been disclosed which is based on the Chinese National Standard (CNS) A4 specification (210X297). 1310376 A7 __ B7 V. INSTRUCTIONS (3 (Please read the note on the back and fill out this page). Contain the deionized water to clean the ion exchange resin until the specific conductivity of the cleaning liquid is 2 5 ° C becomes lower than 50 ° Ώ - 1 / cm, and then the degraded ion exchange resin is dehydrated (refer to Japanese Patent Application Laid-Open No. 1 7 3 8 5 8/1 9 9 7 (Heisei 9 years)); a method comprising rinsing a cation exchange resin with water, followed by phenol cleaning of the resin (see Japanese Patent Application Laid-Open No. 176069/1997 (Heisei 9)): a method which is included in the reactor The sulfonic acid type ion exchange resin is piled up, and then the resin is cleaned with water until the p Η値 of the cleaning waste water becomes 6 or more, and then the resin is cleaned with phenol until the sulfonic acid is removed in the clean phenol. It The concentration becomes 2 p P m or less by weight (see Japanese Patent Application Laid-Open No. 143565/2000 (Heisei 12)), and the like. The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed as described above. It is well known that in acid-type cation exchange resins, water and/or phenolic scrubbing is effective, and the color of the product after the catalyst is charged and after the catalyst is replaced can be maintained by adequate cleaning. However, the current unfavorable situation occurs that it takes a very long time for the water and phenol to be cleaned after the reactor is filled with the catalyst, thereby significantly damaging economic benefits, for example, in the air and in the wet state. In the case of a long-term sulfonic acid type ion exchange resin, a colored eluate containing polystyrene sulfonic acid is included in the pores on the surface and inside. Therefore, it takes a long time to clean. 'The need to simply understand the cleaning performance of the resin, that is, the predicted time required for water and phenol cleaning before the flow system reactor is filled with the sulfonic acid ion exchange resin. -6 - The paper scale 逍China National Standard (CNS) A4 Specification (210X297 mm) 1310376 A7 B7 V. INSTRUCTION DESCRIPTION (4 Inventive Dew in this Case) The general purpose of the present invention is to provide a method for preparing bisphenol A which is based on sulfonate. An acid-type ion exchange resin is prepared from phenol and acetone in the presence of a catalyst, wherein an ion exchange resin which is only required to be cleaned in a short time by a simple method is selected for use in selected applications. Other objects of the present invention will be hereinafter The contents of the disclosed specification become more prominent. In this case, in order to achieve the above object, the inventors have gathered a rigorous, large-scale study and investigation, and as a result, it has been found that the object of the present invention can be used by using a specific simple and clean. The method comprises a cleaning treatment of a sulfonic acid type ion exchange resin, which is treated with ion exchange water and phenol, to finally obtain a sulfonic acid type ion exchange resin having a sulphur content of phenol having a clean phenol of at most 1 p pm, and using the resin Used as a catalyst to form bisphenol. The present invention has been accomplished based on the foregoing findings and materials. In particular, the present invention provides a method for preparing bisphenol A, which is a condensation reaction of a phenol and a ketone in the presence of a sulfonic acid type ion exchange resin as a catalyst and a mercaptan as a co-catalyst, and is characterized in that it is used. a sulfonic acid type ion exchange resin which is ion-exchanged water in a volume of 5 to 20 times the water swelling volume of the resin, and then swelled in a volume of 1 to 3 times the volume of water of the resin in the phenol at 50 to 80 ° Stirring for a period of 2 to 5 hours at a temperature range of C, and solid-liquid separation, wherein the separated phenol for chaifying has a sulfur content of at most one (1) ppm by weight. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ---------·¥-- (Please read the note on the back and fill out this page) Consumer Cooperatives Printed 1310376 A7 _____ B7 V. INSTRUCTIONS (3) It is also possible to fix any thiol to the above sulfonic acid type ion exchange resin and to produce the same effect as the co-catalyst. Read the precautions on the back page and fill in this page. The thiol content used is generally selected from 〇. 1 to 20 moles range 'preferably 1 to 20 moles, based on acetone as the starting material. The ratio of phenol to acetone in the method for preparing bisphenol A of the present invention is not particularly limited, but the content of unreacted acetone is determined from the viewpoints of easiness, economic efficiency and the like for refining the final bisphenol A. It is preferably as small as possible, whereby it is advantageous to use an excess of phenol which is higher than its stoichiometric amount, so that each mole of acetone is usually used in an amount of from 3 to 30 moles, preferably from 5 to 15 moles. In the preparation of bisphenol A, in addition to the reaction liquid is not compatible In the case of a high-viscosity case or a reaction in which the reaction is difficult to perform at a low temperature, for example, a reaction solvent is usually not required. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, is printed in the present invention and uses a continuous multi-stage. A fixed bed reaction system in which phenol, acetone and the aforementioned mercaptan are continuously fed into a reaction column for carrying out a sulfonic acid type ion exchange resin selected by the above simple cleaning method And it only needs to be cleaned in a short time, in the method according to the invention, the cleaning treatment of the sulfonic acid type ion exchange resin charged in the reaction tower is first carried out before the start of the reaction, in the initial step, the water Passing the reaction column packed with the sulfonic acid type ion exchange resin to carry out the cleaning with water until the pH of the discarded clean water reaches about 5.9 to 7', after which the phenol passes through the reaction tower while maintaining the ion The temperature of the exchange resin is in the range of 50 to 80 Å: which substantially replaces the water in the resin with phenol, and thus proceeds to the phenol clean treatment until the phenol is used for cleaning. The sulfur content is applicable to the Chinese National Standard (CNS) 本 specification (210Χ 29*7 DON) on the paper scale. -11 - 1310376 A7 B7 V. Invention description ($weight is changed to 1 P pm. {Please read the back Precautions Refill this page} Subsequently, phenol, acetone and the aforementioned mercaptan are continuously fed into the reaction column for reaction via a continuous fixed bed reaction system. Next, the reaction conditions of the continuous fixed bed reaction system will be described in detail, first, acetone/ The molar ratio of phenol is generally selected in the range of 1/3 0 to 1/3, preferably 1/1 5 to 1/5. When the molar ratio is less than 1/30, it may occur unreasonable. The reaction rate is low, and when the molar ratio is more than 1/3, there is a tendency to cause excessive impurities to form, and the selectivity to bisphenol A is lowered. On the other hand, when the thiol is not fixed on the cation exchange resin, the molar ratio of the thiol/acetone is usually selected in the range of 0.1 / 1 0 0 to 2 0/1 00, preferably 1/1 00. To 1 0/1 00. When the molar ratio is lower than 0 _ 1/1 00, there is a fear of insufficient ability to exhibit sufficient reaction efficiency in terms of increasing the reaction rate or the selectivity to bisphenol A, and when the molar ratio is higher than 2 0/1 At 0 〇, the effect of improving the reaction rate or the selectivity to bisphenol A cannot be confirmed at such a high level. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. In addition, the reaction temperature is usually selected in the range of 40 to 150 °C, preferably 60 to 110 °C. When the reaction temperature is lower than 40 ° C, an unreasonable low reaction rate is generated, and in addition, a reaction liquid having a very high viscosity is generated, so that a curing reaction may occur in this case, and vice versa. When the reaction temperature is higher than 150 ° C, the reaction is difficult to control, the selective attenuation of bisphenol A (p,p '-isomer) and the additional decomposition or attenuation of the cation exchange resin as a catalyst. effect. Usually 'LHSV (Liquid hourly space velocity) is selected in 〇 _ 2 to 3 0 This paper scale applies to China National Standard (CNS) A4 specification (21 〇 X 297 mm) "12 - 1310376 A7 B7 V. Invention description (deduction hr -1 range, preferably from 0.5 to 10 hr -, (please read the back note first and then fill out this page) In the method according to the invention, the reaction mixture from the reaction column can be carried out by a well-known method Post-treatment to collect the target product bisphenol A, which will be described below as a post-treatment example. First, the concentration reaction of the reaction mixture is carried out before crystallization, and the concentration conditions are not particularly limited, but usually include a temperature of 1300-117. The range of 〇 ° C and the pressure is in the range of 13 to 5 3 k P a. When the temperature is lower than 130 ° C, the necessary condition is high vacuum, and when the temperature is higher than 170 ° C , which may cause an increase in the content of impurities or a coloration of the reaction product. It is advantageous to define the concentration of bisphenol A in the concentrated residual liquid at 25 to 40% by weight, but when the concentration is lower than 2 5 At % by weight, it will cause low bisphenol A back Yield, and when the concentration is higher than 40% by weight, it will cause difficulty in slurry transfer after crystallization. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, prints bisphenol A and phenol adduct from concentrated residual liquid. The crystallization is usually carried out by a vacuum cooling crystallization method, the step comprising cooling with latent heat of evaporation by water under reduced pressure. In the above method, the crystallization treatment usually includes a temperature range of 40 to 70 ° C and a pressure of In the range of 3 to 1 3 k P a , about 3 to 20% by weight of water is added to the concentrated residual liquid, and when the water to be added is less than 3% by weight, heat transfer is caused. In addition to insufficient capacity, when the water is higher than 20% by weight, the amount of bisphenol A dissolved and lost will be inappropriately increased. Moreover, when the crystallization temperature is lower than 40 °C, the viscosity of the crystallization liquid may increase. Or the crystallization of the solidification reaction of the crystallization liquid, and when the crystallization temperature is higher than 70 ° C, it will unduly cause an increase in the loss of bisphenol A. -13- This paper scale applies to the Chinese National Standard (CNS) A4 Specifications. (210X297 mm) 13 10376 A7 ___B7 V. Description of the invention (force 1 (please read the notes on the back and fill out this page). Next, the bisphenol A crystallized in the above manner is separated from the phenol adduct by a well-known method, and then phenol is used for hydrazine. Clean and then carried out under conditions where the temperature is usually selected in the range of 1 30 to 200 ° C (preferably 50 to 1 80 ° C) and the pressure is selected in the range of 3 to 20 k P a The chaser-treated adduct is separated into bisphenol A and phenol. The residual phenol in the bisphenol A obtained by the separation treatment is substantially completely removed by a stripping method or the like, thereby Get high quality bisphenol A. In the following, the invention will be described in detail with reference to the accompanying examples and comparative examples, which however, no. Example 1 (1) Simple cleaning test In a 100 ml (m L ) vial, a sulfonic acid type ion exchange resin having a water swelling volume of 5 OmL was fed, and then ion-exchanged water was poured into The total volume is 1 〇OmL, and then the aqueous resin is stirred, allowed to stand, and the upper layer of liquid is extracted to the resin interface printed by the Intellectual Property Office of the Ministry of Economic Affairs. Repeat the same procedure 1 times and filter the cleaned resin under vacuum to remove most of the water. The resin is returned to the above container again, and the phenol is poured into the phenol, and the entire volume including the resin is 10 mL, stirred, allowed to stand, and the upper liquid is taken out to detect the sulfur content therein, and the result is lower than the weight. 1 Ppm. This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) -14 - 1310376 A7 B7 V. Invention description (eg (2) continuous flow test in inner diameter 1 4mm and length 4 5 〇mm The reactor was filled with a volume of 7 OmL of the acid-type ion exchange resin with the previous step, and then the ion exchange water was connected to a flow rate of 10 m L / hr, and the waste enthalpy was detected after 25 hours of simmering for 25 hours. The water of the P water sample on the clean water is shown as neutral 値5. 5. When the water content of the phenol is 0.3% by weight, the temperature is raised to 70 volts and the phenol is flow rate 1 〇m. The resin was dehydrated for 5 hours, at which time the detection result of APHA color was 4 P Pm, and then, under the same conditions as the above-mentioned dehydration reaction, it was treated with 淸 淸, and at the beginning, phenol was cleaned. After 〇 hours, the sulfur content of 酣 decreased to less than 1 P pm by weight, and its APHA color is 1 5 Comparative Example 1 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed stainless steel tube (1) identical Sulfur continues through the reactor, so from the beginning, the result is in the stone, then the resin L / hour through the sulfur content of the antiphenol, and 30 or more (please read the back of the note before refilling this page) (1) The simple chastity test will be the same as the sulfonate ion used in Example 1. The father changed the resin and stored it in the air for 2 months. Then repeat the step of Example 1 (1) 'Collect the upper layer liquid to detect the sulfur content'. The result is 5 pp 2 in the weight of the continuous flow test. The paper scale is applicable to the Chinese country. Standard (CNS M4 specification (210X297 mm) 1310376 A7 -___^ & 'Inventive description (using the same sulfonic acid type ion exchange resin that has been stored in air for 2 months as in the previous step (1) is repeated Example 1 ( 2 Steps (Please read the notes on the back and then fill out this page) Therefore, the P Η値 of the discarded clean water is detected after 25 hours from the start of the cleaning, and the result is neutral 値5 on the litmus paper. 2 After the acid dehydration reaction for 25 hours, the phenolic water content is 0. 3% when the acid sulfur content and its A Ρ ΗΑ color are detected as 8 P pm ' and 30 or more, respectively. Subsequently, it is carried out under the same conditions as the aforementioned dehydration reaction. After treatment with acid, the sulphur content of the phenol dropped to less than 1 p pm by weight after 40 hours from the beginning of phenol cleaning, and its APHA chromaticity was 2 〇 by Example 1 and Comparative Example 1. It can be understood that the relationship between the result of the simple chastity test and the confirmation result of the continuous flow test can be categorically confirmed by the Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed according to the present invention, and the phenol and acetone can be used. Efficient preparation of bisphenol A 'which is prepared by using a sulfonic acid type ion exchange resin as a catalyst in an economically advantageous manner, and which requires only a short period of time for cleaning due to a specific simple cleaning method. -16- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm}