九、發明說明： 【發明所屬之技術領域】 本發明係關;^ ή 1 p 到的酸分解生成物_3=基氫過氧化物之酸分解得 之精製方法。 f雜貝除去，以製造高純度酚類的酚類 又，本發明係關 所得之粗製笨酚中 精製方法。 於自由氫過氧化異丙苯之酸分解生成物 將雜質除去’以製造高純度酚之酚類之IX. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a method for purifying an acid decomposition product of ή 1 p to an acid decomposition product of a base hydroperoxide. The f-shell is removed to produce a phenol having a high purity phenol. Further, the present invention relates to a method for purifying a crude phenol obtained. The acid decomposition product of free cumene hydroperoxide removes impurities to produce phenols of high purity phenol.
【先前技術】 =類Γ、可經由：使燒基苯氧化成烧基芳基&過氧化物之 以萨鰥Μ烷基本之氧化反應生成物濃縮之步驟、使濃縮液 、义觸媒進行裂解反應成為酚類與酮之步驟、使酸裂解生 成物中和之步驟、及將酸裂解生成物蒸餾分離之步驟而予 以製造。 /邻J 丁 紛類之製造方法，已知為例如使藉由異丙苯（c職ne) Φ之氧化得到的氫過氧化異丙苯進行酸分解的方法。此方法 中之酸分解生成物，除了作為主成分之苯酶及丙酉同之外， 亦έ有α曱基本乙細、苯乙酮、久紛（cu町1 phen〇i )、 =一一甲基苯基甲醇、未反應的異丙苯等各種副生成物及 微量的羥丙酮（HA)、苯基丙醛（α_ΡΡΑ)等之各種羰基 化合物。然而，酚類的用途可舉例如使用作為二苯基丙 烧、聚碳酸酯等之製造原料，此等原料乃要求高純度之苯 紛0 此等高純度苯酚’其雜質之羥丙酮（ΗΑ)之含有量必須降 312ΧΡ/發明說明書(補件)/95·06/95】05596 5 丄幻3485 =至如ppm以下，以10ppm以下為佳。又，所含有之其他 月曰肪知及务香私纟反基化合物的總量（Ha以外之總幾基）必 湏減低至l〇〇ppm以下，以減低至5〇卯m以下為佳。 為了得到此種高純度苯酚，須進行下述之精製： 料成物中，將大部分之丙酮、異丙笨、水、卜甲基^ 乙烯等之低沸點物質及苯乙酮、α—二甲基苯基甲醇^之 高彿點物質，藉由分館除去，得到苯刪，#自該苯紛 顧份除去經丙_(ΗΑ)等之脂肪族m基化合物及m丙 醛（α-ΡΡΑ)等之芳香族羰基化合物。 土 m等㈣化合物’尤其難以自苯时除去，因而 將導致製品苯紛的品質不良。 習知之高純度笨酚的精製方法，例如於日本專利特公日刀 = ^64號公報（專利文獻n提案有：藉由將粗製苯齡 (“經丙酮200卿)於職下與活性氧化紹觸媒接 觸’使㈣酮與苯較應成為2-甲基苯并μ㈣βρ)，[Prior Art] = a type of hydrazine, which can be obtained by oxidizing a benzene group to a aryl group of a aryl group and a peroxide, and concentrating the oxidation reaction product of the sulfonyl group, and concentrating the solution and the catalyst. The cleavage reaction is carried out by a step of forming a phenol and a ketone, a step of neutralizing the acid cleavage, and a step of separating and separating the acid cleavage product. A method for producing a mixture of butyl benzoate is known, for example, as a method of decomposing cumene hydroperoxide obtained by oxidation of cumene. The acid decomposition product in this method, in addition to the benzene enzyme and the propyl hydrazine which are the main components, also contains α 曱 basic propyl, acetophenone, long-term (cu cho 1 phen〇i ), = one by one Various by-products such as methylphenylmethanol and unreacted cumene, and various carbonyl compounds such as hydroxyacetone (HA) and phenylpropionaldehyde (α_ΡΡΑ). However, the use of the phenols may, for example, be used as a raw material for the production of diphenylpropane or polycarbonate, and such raw materials are high purity benzenes such as high purity phenols. The content must be reduced by 312 ΧΡ / invention manual (supplement) / 95 · 06 / 95] 05596 5 丄 3 3485 = to below ppm, preferably less than 10ppm. In addition, the total amount of other anti-base compounds (the total number of bases other than Ha) contained in the sputum and the scent of the scented scent must be reduced to less than 10 〇〇 ppm, preferably to be less than 5 〇卯 m. In order to obtain such a high-purity phenol, the following purification is carried out: Most of the low-boiling substances such as acetone, isopropyl, water, and methyl ethylene, and acetophenone and α-dimethyl are present in the composition. Phenyl benzyl alcohol ^ high point material, by the branch to remove benzene, # from the benzene to remove the aliphatic m-based compound such as C- (ΗΑ) and m propionaldehyde (α-ΡΡΑ) An aromatic carbonyl compound. The compound (4) of the earth m or the like is particularly difficult to remove from the benzene, and thus the quality of the product benzene is poor. A conventional method for purifying high-purity phenols, for example, in Japanese Patent Special Japanese Knife = ^64 (patent document n proposal: by using crude benzene age ("Acetone 200 qing") and active oxidation The catalyst contact 'mute the ketone with benzene to be 2-methylbenzo[4]βρ),
^後，以水蒸汽蒸顧使苯紛與2_甲基苯并咬喘分離的方 中揭又右^本專利特公昭5[1289號公報（專利文獻2) 中揭不有於甲齡之精製使用活性氧化㈣方法。 Ϊ專利特公昭42 —1225G號公報（專利文獻 3)中揭不有錯由使粗製苯盼於15Q〜25(rc下與 氧化㈣媒接觸而使職化合物轉化為其他化合物 該化合物與苯酚藉由墓铃 八 ^ 第micm : Γ 的方法。又，於英國專利 第1231991號公報（專利文獻4)中揭示有使不含水的粗制 本紛與酸性離子交換樹脂觸媒於.15(^下接觸，使/ 312XP/發明說明書(補件)/95-〇6/95105596 基化合物轉化為其他化合物後， 蒸餾而分離的方法。 租衣丰紛中之有用成分 "基苯乙烯將與雜質反應，或分別縮合：刀之本齡及 基苯酚及烯烴之2晉彳t &，π t > 成異丙苯 真…r二 有用成分消失等之問題。 ^文獻1.曰本專利特公昭37—1 1 664號公報 專利文獻2.曰本專利特公昭54-1289號公報 f利文獻3 :日本專利特公昭42-12250號公報 專利文獻4 :英國專利第1231991號公報 【發明内容】 (發明所欲解決之問題） ^明之目的在於提供—種_之精製方法， 中之上述問題點’在穩定溫和的反應條；下ί :匕=!烧基芳基氫過氧化物之酸分解生成物或氫過氧^ After the steam steaming, the benzene is separated from the 2_methylbenzene and the gas is separated from the right. The patent is published in the Japanese Patent Publication No. 5 [1289 (Patent Document 2). Purification uses the active oxidation (4) method. ΪPatent Special Publication No. Sho 42-1225G (Patent Document 3) discloses that there is no error in that the crude benzene is expected to be converted into other compounds by contacting the oxidized (tetra) medium with 15Q to 25 (the rc and the phenol). Tomb 八 ^ mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic mic , / 312XP / invention manual (supplement) / 95-〇 6 / 95105596 after the conversion of the base compound to other compounds, the method of separation by distillation. The useful ingredients in the renting of the base styrene will react with impurities, Or condensation: the age of the knife and the phenol and olefin of the 2 彳t &, π t > cumene ... r two useful components disappeared. ^ Document 1. 曰本专利特公昭37 _1 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The problem to be solved) _ Kind of purification method, the above-described problems in the 'stable mild reaction conditions; the ί:! = Dagger burning aryl hydroperoxide decomposition product of an acid or hydroperoxide
再使該化合物與笨酚藉由 然而 於上迷方法 質顯=酸分解生絲的粗製絲、與對其所含有的雜 二=咖族或第VIIB族金屬氧化物接觸， 點介a你用*成刀消失，且使雜質之羰基化合物轉化為高沸 :^ ’藉由蒸餾使該高沸點化合物與酚類分離 向純度酚類。 (解決問題之手段） 亦即，依據本發明之第1發明，提供： 处種酶類之&製方法’其為使藉由烧基芳基氫過氧化物 =刀解得到之酸分解生成物、與第族或第v 11B族金 匕物接觸’使烧基芳基氫過氧化物之酸分解生成物中 12Χ^®__)/95•議1〇55% 7 1333485 的脂肪族幾基化合物及/或芳香族隸基化 彿點之化合物，然後藉由蒸館將此ϋ為更问 分離。 c寺间/弗點化合物與酚類 又’依據本發明之第2發明， 於第1發明的酚類之精製方法中，對藉 #、 氧酸分解得到之酸分解生成物添加驗:; 巩乱胆〆、存下與選自第VB族及第VIIB族金屬氧化物: 1種以上所構成的金屬氧 感乳化物中之 物之酸分解生… 使烧基芳基氫過氧化 文刀解生成物中之脂肪族羰基化合物及/或芳香族# 基化合物轉化為争古、.故科々儿人 " 、'手反 後，與由b 物’然後將反應液中和 猎由蒸鶴將該高滞點化合物與盼類分離。 又’依據本發明之第3發明， 於第1或第2發明之酉分類之精製方 氧化物為選自氫過氧化显而焚卜卜 兀基方基11過 化仲丁Μ 虱過氧化乙基苯、氫過氧 之至少過氧化異丙甲笨及氣過氧化二異丙基笨令 二;發明之！4發明’於第1至第3發明之紛 笨’酚類為苯酚。 軋化物為氫過氧化異丙 又’依據本發明之莖ςIB .. ^ _之精製方法中鹼水::為： 氧化鋼類水溶液中之氮 水溶液及苯 聊發明說明書(補件)/95-06/95105596 紛:之:::::之第6發明，於第2至第5發明之任一 月衣法令’添加用以使酸分解生成物之pH維持 丄 W485 於約4〜12之有效量的鹼水溶液。 又’依據本發明之第7發明 方法中，使藉由烧基芳基氫過:化:二 成物、與選自第"族及第㈣族金屬 接觸。 太^上所構成的金屬氧化物，於50〜150t下 方法中依Π:、明之第8發明，於第1發明之酚類之精製 笨VBH化異丙苯的酸分解生成物得到之粗製 f , 矢或第¥118族金屬氧化物觸媒接觸，使粗 物妙、之脂肪族幾基化合物轉化為更高沸點之化合 後藉由蒸餾將此等高滩點化合物與酚類分離。 方：中依1!本發：之第9發明’於第δ發明之_之精製 粗製苯酚與金屬氧化物觸媒在溫度100〜25(Tc 下接觸30〜i8〇分鐘。 -I:依據本發明之第10發明，於第1至第9發明之任 選自製方法中’第VB族及第νιΐΜ金屬氧化物為 、 銳、叙、猛及銖所構成群之金屬氧化物。 一又、依據本發明之第11發明，於第1至第10發明之任 ，頦之精製方法中，於金屬氧化物接觸處理後自反應生 物勿之酚類的瘵餾分離，為水蒸汽蒸餾或有機溶劑萃取蒸 (發明效果） 依據本發明之方法，藉由使烷基芳基氫過氧化物之酸分 生成物與特定金屬氧化物接觸，可於抑制有用成分之酚 312XP/發明說明書(補件)/95-06/95105596 9 1333485Further, the compound and the phenol are contacted by the above method, the acid is decomposed into the crude filament of the raw silk, and the hetero bis = gamma or the VIIB metal oxide contained therein is contacted. The resulting knife disappears and the carbonyl compound of the impurity is converted to a high boiling point: the high boiling point compound is separated from the phenol by the distillation to the purity phenol. (Means for Solving the Problem) In other words, according to the first aspect of the present invention, there is provided a method for producing an enzyme, which is produced by decomposition of an acid obtained by calcining an aryl hydroperoxide = knife solution. Contact with the group or the v 11B gold sputum 'Is the acid decomposition of the aryl aryl hydroperoxide 12 Χ ^ ® __) / 95 • 1 1 55% 7 1333485 aliphatic group Compounds and/or aromatic ligated compounds of the stagnation point, and then the sputum is separated by the steaming hall. According to the second invention of the present invention, in the method for purifying the phenol according to the first aspect of the invention, the acid decomposition product obtained by decomposing #, oxyacid is added to the test; The acid decomposition of a metal oxide oxidant selected from the group consisting of Group VB and Group VIIB metal oxides: one or more kinds of metal emulsifiers... The aryl aryl hydroperoxide solution The aliphatic carbonyl compound and/or aromatic #-based compound in the product is converted into the sacred ancient, and the scorpion ", the 'hand back, and the b thing' and then the reaction liquid is neutralized by the steaming crane The high hysteresis compound is separated from the desired class. Further, according to the third invention of the present invention, the refined cerium oxide classified according to the first or second invention is selected from the group consisting of hydroperoxide and incineration. Hydrogen peroxide, at least oxidized isopropanol and gas peroxide diisopropyl stupid; invented! 4 invention "The phenols of the first to third inventions are phenol". The rolled product is isopropyl hydroperoxide and the stalk ς according to the present invention IB.. ^ _ the method of refining the alkali water:: is: the aqueous solution of the nitrogen in the oxidized steel aqueous solution and the benzene talk instructions (supplement) / 95- 06/95105596: The sixth invention of the following:::::, in any of the second to fifth inventions, the addition of the pH for maintaining the acid decomposition product 丄W485 is effective at about 4 to 12 A quantity of aqueous alkali solution. Further, according to the seventh invention of the present invention, the aryl group is hydrogenated to form a dimer, and is contacted with a metal selected from the group " and the group (4). In the method of 50 to 150 volts, the metal oxide formed in the above-mentioned method is based on the eighth invention of the invention, and the crude product of the acid decomposition product of the purified phenolic phenol of the first invention is obtained. , or the Group 118 metal oxide catalyst is contacted to convert the crude fatty group compound into a higher boiling point and then separate the high beach compound from the phenol by distillation. Fang: Zhongyi 1! The hair of the ninth invention of the ninth invention of the δ-invention of the crude phenol and the metal oxide catalyst at a temperature of 100 to 25 (Tc contact 30~i8 〇 minutes. -I: according to the present According to a tenth aspect of the present invention, in the method of any one of the first to ninth aspects, the metal oxide of the group VB and the νιΐΜ metal oxide is a group of the group consisting of sharp, ruthenium, turmeric and ruthenium. According to an eleventh aspect of the present invention, in the method for purifying a ruthenium according to the first aspect of the present invention, after the metal oxide contact treatment, the phenol is separated from the reactive biological phenol, and the steam is distilled or the organic solvent is extracted. Steaming (Effect of the Invention) According to the method of the present invention, by contacting an acid fraction of an alkylaryl hydroperoxide with a specific metal oxide, the phenol 312XP/invention specification (supplement)/ 95-06/95105596 9 1333485
類及烯苯的消失之下，於溫和的反應條件下使所含有的 質之脂肪族羰基化合物及/或芳香族羰基化合物轉化為 彿點化合物。 又，依據本發明之方法，藉由使由氯過氧化異丙苯的酸 分解生成物所得之粗製苯酚與特定的金屬氧化物觸媒接 觸’可於抑制有用成分之苯酚及α —甲基笨乙烯的消失之 下，於溫和的反應條件下’使含有的雜質之 合物轉化為高沸點化合物。 土化 然後，自上述尚沸點化合物藉由蒸餾將酚類分離，可容 易地製造高純度酚類。 【實施方式】 本土月中作為精製對象之酸分解生成物，為例如將藉由 異丙苯之氧化反應所得之氫過氧化異丙苯進行酸分解的 生成物’其組成如下述： 29· 〇~46. 1% 47. 〇〜36· 0% u.卜 7. 8% 4. 5〜1. 2% 丙嗣Under the mild reaction conditions, the aliphatic carbonyl compound and/or aromatic carbonyl compound contained therein is converted into a smectite compound under the mild reaction conditions. Further, according to the method of the present invention, by contacting the crude phenol obtained by decomposing the acid of cumene chloroperoxide with a specific metal oxide catalyst, phenol and α-methyl are inhibited from the useful components. Under the disappearance of ethylene, the compound containing the impurities is converted into a high-boiling compound under mild reaction conditions. Soilification Then, the phenols are separated by distillation from the above-mentioned boiling point compounds, and high-purity phenols can be easily produced. [Embodiment] The acid decomposition product to be purified in the local month is, for example, a product obtained by acid decomposition of cumene hydroperoxide obtained by oxidation reaction of cumene, and its composition is as follows: 29· ~46. 1% 47. 〇~36· 0% u. Bu 7.8% 4. 5~1. 2% 嗣
苯紛 異丙苯 α -甲基笨乙烯 其他 Uu ¢1% 一本毛月中，作為精製對象之粗製苯酚，係將異丙苯 氧化反應所得之氫過氧化異丙苯進行酸分解，自其酸分 解生成物的中和物中，胳办I丨上工 — 寻例如丙酮、異丙苯、水、α _曱 基本乙稀等低沸點物質之大 ^ ^ 心大邛分及笨乙酮、α-二甲基苯 基曱醇專南 >弗點物質之大八八 貝大。Ρ分分別蒸餾而製得。粗製笨酚 312ΧΡ/發明說明書(補件)/95-06/95105596 中之α-甲基苯乙稀的旦 於上述酸分解生成物或：/苯下為佳。 其他脂肪族幾基化合物、芳香：:二，_ 之雜質。 方晋私叛基化合物及其他化合物 二=中屬=媒使用之金屬氧化物為第VB族及第 及銶所構成 屮.=备儿 孟屬的减物。其等之具體例，可舉 ΐΏ · 一乳化—鈒、四氧务一如 三氧化二銳、二氧化纪^ 叙、一氧化銳、 鈕、五ίι各- "氧化一鈮、—氧化鈕、二氧化 二2 鈕、一氧化錳、四氧化三錳、三氧化二錳、 一：、、七氧化二錳、-氧化二銖、-氧化銖、三氧化 氧化銖、五氧化銖、三氧化錁、七氧化二銖等， /佳者可使用二氧化鐘、四氧化三料之鐘氧化物 五氧化一鈒等之鈒氧化物。此外，亦可使用混合2種以 上上述金屬之複合化合物。 本發明中，金屬氧化物可直接使用粉末狀者，亦可使其 載持於蜂巢狀或粒狀等之氧化銘、二氧化碎或二氧化石夕― 氧化紹載體，或將金屬氧化物本身成形為此等形狀而使 用。 本發明中，較佳為對前述烷基芳基氫過氧化物之酸分解 生成物在含氧氣體環境條件下添加氫氧化鈉水溶液或苯 氧化鈉類水溶液，藉由使該酸分解生成物與上述金屬氧化 物觸媒接觸’使酸分解生成物中的脂肪族羰基化合物及/ 或芳香族羰基化合物在溫和的反應條件下轉化為高沸點 312XP/發明說明書(補件)/95〇6/951 〇5596 11 1333485 Μ 〇 15。。。為宜，較佳為於加 =1130㈣態下，於含氧氣體共存下之大氣 ，使其與金屬氧化物觸媒接觸。接觸時間以5.分 、，且，尤以1 〇〜3 0分為佳。通常，於高、、丄 刀 係以較短時間為佳，於低溫、㈣；二形下 為佳。 係以較長時間 接法'連續法等任意方法 觸媒填充層可為流動床，亦可為固定床。 驗水溶液調整PH的酸分解生成物通過觸絲充層之、:、° 速’以贿卜版-!為適當，尤以_2★曰 錯由在此反應條件下與觸媒接觸，酸分解生成 :酮:⑷等之脂肪族羰基化合物及α _笨基丙醛工 =芳香族幾基化合物、其他之㈣化合物將轉化為較並 南〉弗點的多量體或氧化生成物等之化合物。此時，苯齡、、 α-甲基苯乙烯等有用成分幾乎沒有消失。理由在於 為觸媒使用之金屬氧化物於脂肪族㈣化合物及芳香族 羰基化合物的轉化上顯示出特有的活性，且藉由以氫氧化 鈉水溶液或苯氧化鈉類水溶液調整反應時的ΡΗ，將大椤 促進此等反應而可於溫和的反應條件下得到高轉化率。田 又’於本發明中’藉由使得自前述氫過氧化異丙苯的酸 分解生成物之粗製苯酚與上述金屬氧化物觸媒接觸，可將 粗製苯齡中之脂肪族幾基化合物轉化為高沸點化合物。亦 即，使粗製苯齡加熱至飢以上（以100〜25(rc為佳）的狀 態下’於大氣塵或加麗下，與金屬氧化物接觸。接觸時間 3 J 2XP/發明說明書(補件)/95-06/95 ] 05596 1333485 制:广。分為宜，以， 二:下形下以短時間接觸為佳，於低溫二 日。滑形下則以長時間接觸為佳。 低& 此時，接觸方法並無限制， 方法接觸。又，觸媒填充層可法;^法等任意 使粗製笨粉通過觸媒填充声：：：動t;:可為固定床。 $ a 兄層之流速，以LHSV6〜0. 3hr*-丨生 、田，尤以LHSV2〜0. 5hr-1為佳。 :由與上述般之金屬氧化物觸媒之接觸 ㈤等脂肪族幾基化合物及其他雜質將轉::較之 :喊點之多量體等之化合物，例如，3,3,5_三甲基為夂 。及4-異戊基環己酮等。此時苯齡、“ ^ = 用成分幾乎沒有消失。宜理出祕、，Τ基本乙烯#有 之金屬氧化物顯一屮#/、 ’推》則§忍為係作為觸媒使用 乳化I員不出對脂肪族羰基化合物的轉化之特有 /舌性，而無酸觸媒般的酸強度之故。 錯由與上述金屬氧化物觸媒的接觸，酸分解生成Benzene cumene α-methyl stupid ethylene other Uu ¢ 1% In a Maoyue, the crude phenol to be purified is acid-decomposed by cumene hydroperoxide obtained by oxidation of cumene. In the neutralization of the acid decomposition product, I work on the job - looking for a large amount of low-boiling substances such as acetone, cumene, water, α-曱 basic ethylene, etc. Alpha-dimethylphenyl decyl alcohol special south > gt; The mash is obtained by distillation separately. The α-methylstyrene in the crude phenol oxime 312 ΧΡ / invention specification (supplement) / 95-06/95105596 is preferably the above acid decomposition product or: / benzene. Other aliphatic compounds, aromatic:: two, _ impurities. Fang Jin private base compound and other compounds 2 = medium genus = medium used in the metal oxide is composed of the VB group and the second 屮. = preparation of the genus Mongol. Specific examples thereof include: emulsification - hydrazine, pentoxide, oxidization, oxidization, oxidization, oxidization, oxidization, oxidation, oxidization , 2D dioxide, manganese monoxide, trimanganese tetraoxide, dimanganese trioxide, a:, manganese dimanganese oxide, antimony oxide, antimony oxide, antimony trioxide, antimony pentoxide, antimony trioxide锞, bismuth hexoxide, etc., / can use the oxidized cerium oxide, oxidized cerium oxide, etc. Further, a composite compound in which two or more of the above metals are mixed may be used. In the present invention, the metal oxide may be used as it is, or it may be carried in a honeycomb or granulated form, such as an oxide, a sulphur dioxide or a sulphur dioxide, or a metal oxide itself. It is used for forming such shapes. In the present invention, it is preferred that the acid decomposition product of the alkylaryl hydroperoxide is added with an aqueous sodium hydroxide solution or a sodium benzoate aqueous solution under an oxygen-containing gas environment, whereby the acid is decomposed to form a product. The above metal oxide catalyst contact 'transforms the aliphatic carbonyl compound and/or the aromatic carbonyl compound in the acid decomposition product into a high boiling point under mild reaction conditions 312XP / invention specification (supplement) / 95 〇 6 / 951 〇5596 11 1333485 Μ 〇15. . . Preferably, it is preferably in contact with the metal oxide catalyst in an atmosphere in which the oxygen-containing gas coexists in the state of addition of =1130 (quad). The contact time is divided into 5. points, and, especially, 1 〇 to 3 0 is good. Generally, it is preferable to use a high-speed, high-speed knife, and a low temperature, (four); Any method such as continuous method can be used for a long time. The catalyst filling layer can be a fluid bed or a fixed bed. The aqueous solution is adjusted to adjust the pH of the acid decomposition product through the touch-wire layer: °, speed 'brieze version-! is appropriate, especially _2 ★ 曰 wrong contact with the catalyst under the reaction conditions, acid decomposition Formation: a ketone: an aliphatic carbonyl compound of (4) or the like, and an α-stanopropionaldehyde=aromatic compound, and the other compound (4) is converted into a compound such as a polyvalent body or an oxidation product. At this time, the useful components such as benzene age and α-methylstyrene hardly disappeared. The reason is that the metal oxide used for the catalyst exhibits a specific activity in the conversion of the aliphatic (tetra) compound and the aromatic carbonyl compound, and the hydrazine at the time of the reaction is adjusted by an aqueous solution of sodium hydroxide or sodium benzoate. Euphorbia promotes these reactions and provides high conversions under mild reaction conditions. In the present invention, the aliphatic phenolic compound in the crude benzene age can be converted into a crude phenol from the acid decomposition product of the cumene hydroperoxide and the above metal oxide catalyst. High boiling point compound. That is, the crude benzene age is heated to above hunger (in the state of 100 to 25 (rc is preferred), in contact with the metal oxide under atmospheric dust or galvanized. Contact time 3 J 2XP/invention manual (supplement) ) /95-06/95 ] 05596 1333485 System: wide. Divided into appropriate, to, two: lower contact with short time is better, at low temperature for two days. Under sliding, it is better to contact for a long time. Low & At this time, there is no restriction on the contact method, and the method is contacted. In addition, the catalyst filling layer can be used; the method can be used to fill the rough powder through the catalyst::: t:: can be a fixed bed. The flow rate of the layer is LHSV6~0. 3hr*-丨生,田, especially LHSV2~0. 5hr-1. : Contact with the above metal oxide catalyst (5) and other aliphatic compounds and Other impurities will be transferred:: Compared with: a large number of compounds such as 3,3,5-trimethyl is hydrazine, and 4-isopentylcyclohexanone, etc. At this time, benzene age, "^ = The ingredients have almost disappeared. It is reasonable to know the secret, Τ basic ethylene #有金属氧化显一屮#/, '推推】 § forbearance as a catalyst to use emulsification I can not be fat The specific carbonyl compound conversion / tongue resistance, without an acid catalyst like so that the acid strength. Mistake by the contact with the metal oxide catalyst, decomposition of the acid
粗製苯时的m基雜質轉化為前述般之高彿點化合物，= 此等於後段的蒸餾中可容易地與紛類分離，而可 度苯齡。蒸館分離的方法可暴屮走茧* * 间'' 取蒸餾等。 7舉出水…飽、有機溶劑萃 (實施例） 其次，就本發明之方法舉出實施例具體地說明。於 例中’雜質之各種幾基化合物及主成分係藉由氣相色 析等予以定量，求出處理前後之各雜質的濃度。s刀 [比較例1 ] 3 ] 2XP/發明說明書(補件)/95-06/95105596 13 1333485 使用對氫過氧化異丙苯的酸分解生成物添加氫氧化鈉 水溶液調整為PH7之粗製酸分解生成物作為原二。該粗制 酸分解生成物的組成為丙酮42. 0%、異丙苯} 〇 厂衣 甲基苯乙烯2.0%、苯酚37. 5%、水5. 〇%、羥丙綱。α (HA)l〇〇〇Ppm、α-苯基丙醛（a_ppA)12〇〇ppm、其他 2 竹〇。 、將此粗製酸分解生成物60.0g置入1〇〇ml不銹鋼製高壓 爸中，使高壓釜内以空氣加壓成05Mpa後，於攪拌^慢 慢加熱，於溫度10CTC下反應3〇分。對得到之生成物^ 行分析，結果為 HA 970ppm、α -PPA li〇〇ppm。 [比較例2 ] 將上述粗製酸分解生成物58.2g與苯氧化鈉水溶液（濃 度30. 2%)1· 8g混合，置入100ml的不銹鋼製高壓釜中。 此時的混合液之pH為約1〇.3。然後，使高壓釜内以空氣 加壓成0.5Mpa後，於攪拌下慢慢加熱，於溫度8〇。〇下1 應30分。對得到之生成物進行分析，結果為“π卟卯， α -PPA 800ppm 。 [貫施例1 ] 將上述酸分解生成物55. 2g與苯氧化鈉水溶液丨以的 ，合液（PH10.3)及二氧化錳3.0g置入1〇〇ml的不銹鋼製 高壓釜中。然後，使高壓爸内以空氣加壓成〇5Mpa後， 於攪拌下慢慢加熱，於溫度8(rc下反應3〇分。對得到之 生成物進行分析，結果為HA 1〇ppm、α _ppA 8〇ppm。又， 未確認到有α-曱基苯乙烯之2量體及異丙苯基苯酚的生 成。可得知：如此藉由添加二氧化錳’可在有用成分不會 312χΡ/發明說明書(補件)/95-06/95105596 1333485 •消失下大幅減少雜質之羰基化合物。 [實施例2] 於實施例1中，除了用五氧化釩代替二氧化錳之外，其 .餘係與實施例1同樣地進行反應。對得到之生成物進行分 •析之結果，為HA 9ppm、α -PPA 70ppm。未有α _甲基苯 =烯之2量體及異丙笨基苯酚的生成。如此，五氧化釩亦 、得到與二氧化猛大致同等的結果。 [實施例3]The m-based impurity in the case of crude benzene is converted into the above-mentioned high-fossil compound, which is equal to the separation in the latter stage and can be easily separated from the aliquot, and can be benzene-aged. The method of separation of steaming hall can be violently walked * * between '' taking distillation and so on. 7: Water, saturated, organic solvent extraction (Examples) Next, examples of the method of the present invention will be specifically described. In the examples, the various base compounds and main components of the impurities were quantified by gas phase chromatography or the like to determine the concentration of each impurity before and after the treatment. s knife [Comparative Example 1] 3 ] 2XP/Invention Manual (Supplement) / 95-06/95105596 13 1333485 Adding aqueous sodium hydroxide solution to the acid decomposition product of cumene hydroperoxide to adjust the crude acid decomposition to PH7 The product is the original two. The composition of the crude acid decomposition product is acetone 42.0%, cumene} 〇 plant methyl styrene 2.0%, phenol 37. 5%, water 5. 〇%, hydroxypropyl. α (HA) l〇〇〇Ppm, α-phenylpropanal (a_ppA) 12〇〇ppm, and other 2 bamboo shoots. 60.0 g of this crude acid decomposition product was placed in a high-pressure dad of 1 〇〇ml stainless steel, and the inside of the autoclave was pressurized to 05 Mpa, and then heated slowly while stirring, and reacted at a temperature of 10 CTC for 3 minutes. The obtained product was analyzed and found to be HA 970 ppm and α-PPA li〇〇 ppm. [Comparative Example 2] 58.2 g of the above crude acid-decomposed product was mixed with a sodium benzoate aqueous solution (concentration: 30. 2%) (1 g), and placed in a 100 ml stainless steel autoclave. The pH of the mixed solution at this time was about 1 〇.3. Then, the inside of the autoclave was pressurized with air to 0.5 MPa, and then slowly heated under stirring at a temperature of 8 Torr. Your armpit 1 should be 30 points. The obtained product was analyzed and found to be "π 卟卯, α -PPA 800 ppm. [Example 1] The above-mentioned acid decomposition product was 55.2 g of an aqueous solution of sodium benzene oxide, and the solution was mixed (pH 10.3). And 3.0 g of manganese dioxide was placed in a 1 〇〇ml stainless steel autoclave. Then, the high pressure dad was pressurized with air to 5 MPa, and then slowly heated under stirring to react at a temperature of 8 (rc) The obtained product was analyzed and found to be HA 1 〇 ppm and α _ ppA 8 〇 ppm. Further, the formation of α-mercapto styrene and cumyl phenol were not confirmed. It is known that by adding manganese dioxide, the carbonyl compound of the impurity can be greatly reduced under the disappearance of the useful component 312 χΡ / invention specification (supplement) / 95-06/95105596 1333485. [Example 2] In Example 1 In addition, vanadium pentoxide was used instead of manganese dioxide, and the rest of the reaction was carried out in the same manner as in Example 1. As a result of the separation and analysis of the obtained product, HA 9 ppm and α-PPA 70 ppm were not obtained. Α-methylbenzene = alkene 2 and isopropyl phenol are formed. Thus, vanadium pentoxide is also Meng dioxide to a substantially equivalent results. [Example 3]
將上述粗製酸分解生成物5丨· 〇g與苯氧化鈉水溶液 6. 〇g的混合液（ρΗ1〇. 8)及二氧化錳3. 〇g於空氣環境氣體 下置入1 00ml的不銹鋼製高壓爸中。然後，將此高壓釜密 閉後，於攪拌下慢慢加熱，於溫度丨丨〇t：下反應3()分。 對传到之生成物進行分析，結果為HA 5ppm以下、α -PPA 50 ppm。又，未確認到有α_甲基苯乙婦之2量體及異丙苯 基苯酚的生成。 鲁[貫施例4 ] 使實施例3中得到之反應混合物靜置，使反應液與二氧 化Ιέ刀離。然後’將上述得到之除去反應液的二氧化猛、 •與新調製之上述粗製酸分解生成物51. 〇g與苯氧化鈉水 • 溶液6. 〇g的混合液於空氣環境氣體下置入100ml之不銹 鋼製尚壓爸中。將高壓蚤密閉後’於邊授拌下慢慢加熱， 於溫度11(TC下反應30分。對得到之生成物進行分析， 結杲為HA 5ppm以下、α -PPA 56ppm。又，未確認到有α -甲基苯乙烯之2量體及異丙苯基苯酚的生成。可得知： 312ΧΡ/發明說明書(補件)/95·06/95105596 15 1333485 如此二次反覆使用二氧化錳，亦未見到二氧化錳觸媒之性 能降低。 [實施例5] . 重複8次實施例4之反應操作。對得到之生成物進行分 -析，結果為HA 5ppm以下、ο: -PPA 54ppm。又，未確認到 •有曱基苯乙烯之2量體及異丙苯基苯酚的生成。如此 -8人反覆使用—氧化猛，亦未見到二氧化鐘觸媒之性能降 低。 _ [實施例6 ] 於將氫過氧化異丙苯的酸分解生成物中和後，進行蒸 餾，將丙酮、水、異丙苯及α_曱基苯乙烯之低沸點物的 大部分、與苯乙酮及α -二曱基甲醇之高沸點物的大部分 除去’藉此製得粗製苯紛。得到之粗製苯紛含有〇. 3重量 %之HA、1〜2重量％之〇;-曱基苯乙烯及以全羰基（換算為亞 異丙基丙酮（mesityl oxide))計之其他羰基化合物〇. 2重 • 量％。 將此粗製苯酚50g置入100ml的不銹鋼製高壓爸中，再 添加叙狀的一氧化猛1 g ’使南壓蒼内以氮取代後’於攪 : 拌下慢慢地加熱，於溫度170°C下反應2小時。對得到之 -生成物進行分析，結果為5ppm以下，全羰基為3〇ppm 以下。又，2-甲基苯并呋喃之生成量對ha為不超過0.5 莫耳％’又，未確認到有α-甲基苯乙烯之2量體及異丙苯 基苯紛的生成。 [實施例7] 312ΧΡ/發明說明書(補件)/95-06/95105596 16 1333485 盆餘二6 +除了用四氧化二結代替二氧化鐘之外， ^ ^施例6同樣地進行反應。其結果，Μ為5卿 下，王叛基為30ppm以下。又，2>甲其梦 吾知挪# Th a r基本并°夫喃之生成The above crude acid decomposition product 5丨·〇g and a sodium benzoate aqueous solution 6. 〇g mixture (ρΗ1〇. 8) and manganese dioxide 3. 〇g is placed in an air atmosphere of 100 ml stainless steel High pressure dad. Then, after the autoclave was sealed, it was slowly heated under stirring, and reacted at a temperature of 丨丨〇t: 3 (). The product thus obtained was analyzed and found to be HA 5 ppm or less and α -PPA 50 ppm. Further, the formation of α-methylphenidene 2 and cumylphenol was not confirmed. Lu [Case 4] The reaction mixture obtained in Example 3 was allowed to stand, and the reaction liquid was separated from the cerium dioxide. Then, the above-mentioned crude acid-decomposing solution obtained by removing the reaction liquid and the newly prepared crude acid decomposition product 51. 〇g and sodium phenoxide water • solution 6. 〇g mixture is placed under air atmosphere 100ml stainless steel is still under pressure. After the high pressure crucible was sealed, it was slowly heated under the mixing of the mixture, and the reaction was carried out at a temperature of 11 (TC for 30 minutes. The obtained product was analyzed, and the crucible was HA 5 ppm or less and α -PPA 56 ppm. Further, it was not confirmed that there was The formation of α-methylstyrene and the formation of cumylphenol. It can be known that: 312ΧΡ/invention specification (supplement)/95·06/95105596 15 1333485 The performance of the manganese dioxide catalyst was lowered. [Example 5] The reaction operation of Example 4 was repeated 8 times, and the obtained product was subjected to fractionation analysis, and as a result, HA 5 ppm or less and ο: -PPA 54 ppm. It was not confirmed that there were two kinds of thiophene styrene and the formation of cumene phenol. So -8 people used repeatedly - oxidized, and the performance of the dioxide catalyst was not reduced. _ [Example 6 After the acid decomposition of cumene hydroperoxide is neutralized, distillation is carried out to make most of the low boilers of acetone, water, cumene and α-mercaptostyrene, and acetophenone and α. - removal of a large portion of the high boiling point of dimercapto methanol to 'produce crude benzene. Obtain crude benzene Containing 〇. 3 wt% of HA, 1-2 wt% of hydrazine; - mercaptostyrene and other carbonyl compounds in terms of total carbonyl (converted to mesityl oxide). The amount of the crude phenol 50g was placed in a 100ml stainless steel high-pressure dad, and then added the oxidized fission 1 g ', so that the south pressure is replaced by nitrogen, then the mixture is slowly stirred and heated. The reaction was carried out at a temperature of 170 ° C for 2 hours, and the obtained product was analyzed to find that the total carbonyl group was 3 ppm or less, and the total amount of 2-methylbenzofuran was not more than 0.5. Ear %', the formation of α-methylstyrene and the formation of cumene benzene were not confirmed. [Example 7] 312 ΧΡ / invention specification (supplement) / 95-06/95105596 16 1333485 In addition to using the oxidized two junction instead of the oxidized clock, ^^6 is reacted in the same manner as in Example 6. As a result, the Μ is 5 qing, and the Wang reneke is 30 ppm or less. Also, 2> I know that the ## ar basic and the generation of the fuss
里相對於HA為0.5莫耳％，又，未確認到有Q 烯之2量體及異丙苯基苯酚的生成。 土本 [實施例8] 於實施樹’除了用五氧化二釩代替二氧化錳之外， 其餘係與實施例6同樣地進行反應。其結果，ηα為5_ 以下，全羰基為30ppm以下。又，2_甲基苯并呋喃之生 量相對於HA為1.5莫耳％，又，未確認到有〇_甲基苯乙 稀之2量體及異丙苯基苯酚的生成。 土 [比較例3] 於實施例6 +，除了以酸度函數為Hr氫交換 絲光沸石（mordernte)型沸石之外，其餘係與實施例6同 樣地進行反應。其結果，2-甲基苯并㈣的生成量相對於 鲁HA為7〇莫耳％，α-曱基苯乙烯為全量縮合或聚合。 [比較例4 ] 於貫施例6中，除了以酸度函數調整為+ 4. 〇 $ Η()〈 6之 • 7 _氧化鋁之外，其餘係與實施例6同樣地進行反應。其 •結果，反應液中的HA為2000ppm，可知反應未充分進行。 [比較例5 ] 於實施例6中除了用陽離子交換樹脂（Amberlyst-15R) 代替二氧化錳，且反應溫度設定為12〇〇c之外，其餘係與 實施例6同樣地進行反應。其結果，2-曱基苯并呋喃的生 312XP/發明說明書(補件)/95-06/951055% 17 1333485 成量相對於HA為90莫耳％，α -曱基苯乙烯為全量縮合或 聚合。It was 0.5 mol% with respect to HA, and the formation of the Q-olefin and the production of cumylphenol were not confirmed. Soil [Example 8] The reaction was carried out in the same manner as in Example 6 except that vanadium pentoxide was used instead of manganese dioxide. As a result, ηα is 5 or less, and the total carbonyl group is 30 ppm or less. Further, the amount of 2-methylbenzofuran was 1.5 mol% with respect to HA, and the formation of bismuth-methylphenidene and cumene phenol were not confirmed. Soil [Comparative Example 3] The reaction was carried out in the same manner as in Example 6 except that the mordenite type zeolite was exchanged for Hr hydrogen by the acidity function. As a result, the amount of 2-methylbenzo (tetra) formed was 7 〇 mol % with respect to Lu HA, and α-mercapto styrene was a total amount of condensation or polymerization. [Comparative Example 4] The reaction was carried out in the same manner as in Example 6 except that the acidity function was adjusted to + 4. 〇 $ Η () < 6 7 _ alumina. As a result, the HA in the reaction liquid was 2000 ppm, and it was found that the reaction did not proceed sufficiently. [Comparative Example 5] The reaction was carried out in the same manner as in Example 6 except that the cation exchange resin (Amberlyst-15R) was used instead of manganese dioxide and the reaction temperature was set to 12 〇〇c. As a result, the production of 2-mercaptobenzofuran 312XP / invention specification (supplement) / 95-06 / 951055% 17 1333485 is 90 mol % relative to HA, α - mercapto styrene is a full amount of condensation or polymerization.
312ΧΡ/發明說明書(補件)/95-06/95105596 18312ΧΡ/Invention Manual (supplement)/95-06/95105596 18