201041650 六、發明說明： (一）發明所屬之技術領域 本發明係關於一種將芳族化合物烷化之方法，其包括在包 括固態酸材料與銅之觸媒組成物存在下，以酮與氫反應芳族 化合物。較佳態樣爲，觸媒組成物亦含一或更多種選自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於 . 鐵、釕與餓）、及鑭系元素之元素。特佳態樣爲，觸媒組成 物含一或更多種選自第III A與VIB族元素之元素。 ◎ 特別地’本發明係關於一種以試劑酮、苯與氫開始製造異 丙苯之方法，其在該觸媒系統存在下於單一反應步驟中反應 〇 甚至更特別地，本發明關於一種在含固態酸材料、銅、及 一或更多種選自鉻與鋁之元素之觸媒組成物存在下，以丙酮 與氫將芳族烴（較佳爲苯）烷化之方法，其中固態酸材料包 括或由沸石（較佳爲沸石貝他）組成。 依照本發明之新穎異丙苯製備可特別地用於製造酚之方 Q 法，其包括以下之步驟： (a) 在依照以上指定包括固態酸材料與銅之觸媒系統存在 下，反應苯、丙酮與氫， (b) 將異丙苯氧化成氫過氧化異丙苯， (c) 以酸處理氫過氧化異丙苯，得到其重組成爲酚與丙酮。 較佳態樣爲’用於步驟（a)之觸媒組成物亦含一或更多種選 自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、Vni 族 (限於鐵、釕與餓）、及鑭系元素之元素。特佳態樣爲，步 201041650 驟（a)之觸媒組成物含一或更多種選自第πια與VIB族元素 之元素。 在步驟（〇中形成之丙酮可再循環至步驟（a)用於異丙苯合 成。 依照以上指定’用於步驟（a)之觸媒組成物較佳爲包括沸石 貝他與銅。特佳態樣爲，在步驟（a)中使用含沸石貝他、銅、 及選自鉻與鋁之金屬之觸媒組成物。 (二）先前技術 0 異丙苯或異丙基苯爲基礎化學工業之重要中間物，其主要 作爲製酚之前驅體，酚繼而可作爲製造己內醯胺之中間物， 由其製造耐綸。 酚之工業合成包括苯成爲異丙苯之烷化步驟、異丙苯成爲 氫過氧化異丙苯之氧化步驟、及後續之重組而得酚與丙酮。 目前顧慮的是將苯烷化成異丙苯，磷酸與矽藻土爲主觸媒 (用於固定床反應器）或氟化鋁（A1C13)漿液仍廣泛地用於石 化工業。 Ο 然而，這些方法產生有關環境影響與安全性之問題：事實 上，由於腐蝕、附帶產生毒性有機產物、及消耗觸媒之處置 ，使用這些觸媒特別有問題。 然而，在1 965年，首次發表使用沸石X或沸石Y作爲觸 媒製備異丙苯（Minachevm Kr. M.等人之 Neftekhimiya 5 (1965) 676 ) 。Venuto等人繼而敘述具八面沸石結構之沸石 用於以低碳烯烴（如丙烯）將苯烷化之用途（J. Catal. 5,（1 966) 8 1)° -4- 201041650 美國專利4,292,457敘述ZSM-5型沸石用於以丙烯將苯烷 化之用途。 在使用具貝他型結構之沸石之異丙苯合成已得到有關工 業應用之優良結果，如EP 43 28 1 4專利所述，特別是使用包 括依照EP 68 75 00與EP 847802專利所述之沸石貝他之觸媒 〇 一但得到異丙苯，藉成爲氫氧化異丙苯之氧化步驟，繼而 爲造成過氧化物鍵斷裂形成酚與丙酮之酸處理步驟，將其轉 0 變成酚。 全世界大部份現有製造酚之工業設備作爲基礎之經異丙 苯合成酚造成隨每公斤酚共同製造等於0.61公斤之丙酮量 〇 酚主要用於製造聯酚A (約35%)、酚系樹脂（約35%) 、己內醯胺（約15%)、苯胺、烷基酚、二甲苯酚、及其他 產物，而丙酮主要用於製造甲基丙烯酸甲酯（約45%)、聯 酚A (約20%)、溶劑（約17%)、及甲基異丁基酮（約8% 〇 )。 因此酚與丙酮之需求（至少可能）有固有地源自其共同製 造之不平衡狀況’其無法相對於不同部門之成長差距及兩種 產物之銷售差距而調節其供應。 已提議基於在異丙苯之上游合成中再使用丙酮-隨酚共 同製造一之新穎方法’以避免此狀況。在EP361755專利中 ，由丙酮開始’在以氫還原成異丙醇繼而脫水成爲丙烯後， 完全地或部份地得到用於異丙苯合成作爲苯之烷化劑之丙 201041650 烯。 依照上述方法，再使用用於丙烯再製之可能過量丙酮極爲 麻煩，特別是由於伴隨化學還原轉變成異丙醇及後續將醇脫 水成丙烯之高步驟數量。 減少再使用丙酮之化學轉變數量之替代方案包括在異丙 苯合成中直接使用以氫將丙酮還原而得之異丙醇作爲苯之 . 烷化劑，例如，如EP 1069100專利所述。 由工業觀點，相對於涉及再製作爲苯之烷化劑之丙烯之選 〇 擇，以將隨酚共同製造之丙酮還原而得之異丙醇將苯直接烷 化代表改良，但是由工業與方法觀點，最佳之解決方法顯然 包括在異丙苯合成中在氫存在下直接使用丙酮作爲苯之烷 化劑。 現在已發現可促進直接由試劑丙酮、苯與氫開始合成異丙 苯之觸媒系統。 依照在此申請之工業方法所得之異丙苯繼而可藉由成爲 氫過氧化異丙苯之氧化步驟及氫過氧化異丙苯後續重組成 〇 爲酚與酮，而用於製造酚。如此得到之丙酮繼而可依照在此 申請之工業方法進行以丙酮與氫將苯直接烷化，而用於異丙 苯合成。 (三）發明內容201041650 VI. Description of the invention: (I) Field of the Invention The present invention relates to a method for alkylating an aromatic compound comprising reacting a ketone with hydrogen in the presence of a catalyst composition comprising a solid acid material and copper. Aromatic compound. Preferably, the catalyst composition also contains one or more selected from the group consisting of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, Group VIII (limited to iron, strontium and starvation), and lanthanides. The element of the element. A particularly preferred aspect is that the catalyst composition contains one or more elements selected from Groups III A and VIB elements. ◎ In particular, the invention relates to a process for the production of cumene starting with a reagent ketone, benzene and hydrogen, which reacts in a single reaction step in the presence of the catalyst system, and even more particularly, the invention relates to a method for alkylating an aromatic hydrocarbon (preferably benzene) with acetone and hydrogen in the presence of a solid acid material, copper, and a catalyst composition of one or more elements selected from the group consisting of chromium and aluminum, wherein the solid acid material It comprises or consists of a zeolite, preferably zeolite beta. The novel cumene preparation according to the present invention can be specifically used in the process for producing phenol Q, which comprises the following steps: (a) reacting benzene in the presence of a catalyst system comprising a solid acid material and copper as specified above Acetone and hydrogen, (b) oxidation of cumene to cumene hydroperoxide, (c) treatment of cumene hydroperoxide with acid, which is recombined into phenol and acetone. Preferably, the catalyst composition used in step (a) also contains one or more selected from Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, Vni (limited to iron, bismuth and Hungry, and elements of actinides. A particularly preferred aspect is that the catalyst composition of step 201041650 (a) contains one or more elements selected from the group consisting of elements of the group πια and VIB. The acetone formed in the step (the acetone formed in the crucible may be recycled to the step (a) for the synthesis of cumene. The catalyst composition for the step (a) as specified above preferably comprises zeolite beta and copper. In the case of step (a), a catalyst composition comprising zeolite beta, copper, and a metal selected from the group consisting of chromium and aluminum is used. (b) Prior art 0 cumene or cumene as the basic chemical industry An important intermediate, which is mainly used as a precursor for phenol, and phenol can be used as an intermediate for the manufacture of caprolactam to produce nylon. The industrial synthesis of phenol includes the alkylation step of benzene to cumene, and isopropyl Benzene becomes an oxidation step of cumene hydroperoxide, and subsequent recombination to obtain phenol and acetone. The current concern is to alkylate benzene to cumene, phosphoric acid and diatomaceous earth as the main catalyst (for fixed bed reactor) Or aluminum fluoride (A1C13) slurries are still widely used in the petrochemical industry. Ο However, these methods have problems with environmental impact and safety: in fact, due to corrosion, incidental production of toxic organic products, and consumption of catalysts Use these catalysts in particular However, in 965, the preparation of cumene using zeolite X or zeolite Y as a catalyst was first published (Minachevm Kr. M. et al., Neftekhimiya 5 (1965) 676). Venuto et al. The use of a zeolite of the structure for the alkylation of benzene with a low-carbon olefin such as propylene (J. Catal. 5, (1 966) 8 1) ° -4- 201041650 US Patent 4,292,457 describes the use of ZSM-5 type zeolite Use of propylene to alkylate benzene. The use of cumene in zeolites with a beta-type structure has yielded excellent results in industrial applications, as described in EP 43 28 1 4 patents, especially in accordance with EP 68 75 00. Once the catalyzed catalyst of the zeolite is described in the EP 847802 patent, cumene is obtained, which is an oxidation step of cumene hydroxide, followed by an acid treatment step of causing peroxide bond cleavage to form phenol and acetone. It turns into phenol. Most of the world's existing industrial equipment for the manufacture of phenol is based on the synthesis of phenol from cumene. The amount of acetone, which is equal to 0.61 kg per kg of phenol, is mainly used to make biphenol A. 35%), phenolic resin (about 35 %), caprolactam (about 15%), aniline, alkylphenol, xylenol, and other products, while acetone is mainly used in the manufacture of methyl methacrylate (about 45%), biphenol A (about 20 %), solvent (about 17%), and methyl isobutyl ketone (about 8% 〇). Therefore, the demand for phenol and acetone (at least possible) is inherently derived from the imbalance of its co-production's Adjusting the supply gap in different sectors and the sales gap between the two products. It has been proposed to avoid this by using a new method of co-manufacturing acetone-phenol in the upstream synthesis of cumene. In the EP 361 755 patent, starting from acetone, after reduction to hydrogen isopropanol followed by dehydration to propylene, a C-201041650 olefin for the synthesis of cumene as a benzene alkylating agent is obtained in whole or in part. In accordance with the above process, the reuse of a possible excess of acetone for the re-production of propylene is extremely troublesome, particularly due to the high step number of conversion to isopropanol with chemical reduction and subsequent dehydration of the alcohol to propylene. An alternative to reducing the amount of chemical conversion of the re-use of acetone involves the direct use of isopropanol, which is obtained by reduction of acetone with hydrogen, as the benzene in the synthesis of cumene. For example, as described in EP 1069100. From the industrial point of view, relative to the choice of propylene involved in the re-production of benzene alkylating agent, the direct alkylation of benzene by isopropanol obtained by reduction of acetone co-produced with phenol represents improvement, but by industry and method The best solution is to include the direct use of acetone as the alkylating agent for benzene in the presence of hydrogen in the synthesis of cumene. It has now been found to promote a catalyst system that directly synthesizes cumene from the reagents acetone, benzene and hydrogen. The cumene obtained according to the industrial process of the present application can be used for the production of phenol by the oxidation step of becoming cumene hydroperoxide and the subsequent reconstitution of cumene hydroperoxide to phenol and ketone. The acetone thus obtained can then be directly alkylated with acetone and hydrogen in accordance with the industrial process of this application for cumene synthesis. (3) Invention content
因此’本發明之目的有關一種將芳族化合物烷化之方法， 其包括在包括固態酸材料與銅之觸媒組成物存在下，以酮與 氫反應芳族化合物。較佳態樣爲，觸媒組成物亦含一或更多 種選自第 IIIA、IVA、ΙΠΒ、IVB、VB、VIB、VIIB 族、VIII 201041650 族（限於鐵、釕與餓）、及鑭系元素之元素。特佳態樣爲， 觸媒組成物含一或更多種選自第III A與VIB族元素之元素 。芳族化合物較佳爲苯。 酮較佳爲丙酮。 更特別地’本發明之目的有關一種將苯院化而產生異丙苯 之方法’其包括在含固態酸材料與銅之觸媒系統存在下反應 . 丙酮、苯與氫’其在單一步驟中反應。較佳態樣爲，用於將 苯烷化成異丙苯之觸媒組成物另外含一或更多種選自第 0 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於 鐵、釕與餓）、及鑭系元素之元素。特佳態樣爲，觸媒組成 物含一或更多種選自第ΠΙΑ與VIB族元素之元素，較佳爲 鉻或鋁。 本發明之目的之烷化方法可由從異丙苯製備酚相當簡化 :事實上不必首先進行丙酮成爲異丙醇之化學還原轉變（例 如，如美國專利5,1 60,497所述），繼而將異丙醇化學脫水 轉變成異丙烯（例如，如美國專利5,0 1 7,72 9所述），最後 Ο 以丙烯將苯化學垸化轉變（例如，如ΕΡ 439032專利所述） 〇 上述之化學變化通常在對各討論之反應稍微不同之反應 條件下及同樣地在不同之觸媒存在下進行。 用於本發明方法之觸媒系統可使由試劑丙酮、苯與氫開始 製備異丙苯所需之所有化學變化在單一反應步驟中同時進 行，使異丙苯產率極大化，及使各種試劑、中間物與產物之 次級反應極小化。 -7- 201041650 熟悉此技藝者可預期之決定總產率特別重要爲二次及所 不欲之反應，苯與氫成爲環己烯、環己烷與己烷之平行還原 反應、丙酮成爲4-甲基-3-戊烯-2-酮之平行縮合反應、及這 些副產物與主要反應之各種試劑及產物之後續反應，例如， 由於環己烯造成將苯烷化成苯基環己烷、及由於氫造成將4-甲基-3-戊烯-2-酮還原成4-甲基-2-戊酮與4-甲基-2-戊醇。 用於本發明方法之觸媒系統出乎意料地可將試劑轉化成 所需產物，將所不欲產物之形成減至最少。 ¢) 用於芳族化合物（特別是苯）之烷化方法之觸媒系統，其 爲本發明之目的，包括固態酸材料與銅，其中銅較佳爲氧化 物之形式。 依照較佳態樣，觸媒組成物亦含一或更多種選自第ΠΙΑ、 IVA、 ΙΙΙΒ、IVB、VB、VIB、VIIB 族、VIII 族（限於鐵、 釕與餓）、及鑭系元素之元素。這些第IIIA、IVA、IIIB、 IVB、 VB、VIB、VIIB族、VIII族（限於鐵、釕與銨）、及 鑭系之元素較佳爲亦爲氧化物之形式。特別地，銅與這些元 〇 素可以混合氧化物之形式含於觸媒組成物中。 依照特佳態樣，觸媒組成物含一或更多種選自第ΙΠΑ與 VIB族元素之元素。依照以上指定，這些第IIIΑ與VIB族 之元素較佳爲氧化物之形式。特別地，銅與這些元素可以混 合氧化物之形式含於觸媒組成物中。 本發明之特佳態樣爲，使用含銅及選自鉻與鋁之元素之觸 媒組成物。特別地，銅與這些元素可以混合氧化物之形式含 於觸媒組成物中。 201041650 特別地，銅與鉻可以鉻礦銅之形式含於觸媒組成物中。鉻 礦銅以實驗式CuO_CuCr2〇4表示。CuCr2〇4已知爲C.A.S. R.N. 12018-10-9 且欽述於”Gmelins Handbuch der Anorganischen Chemie，第 8 版，Vol. Kupfer，第 b 部，Installment 3，系 統號碼60’第60頁”。在本發明之方法中，可使用稱爲鉻礦 銅之商業可得材料，其含Cu (II)與Cr (III)，具有不同比例 之CuO與CuCr204。這些材料對熟悉此技藝者爲已知的，其 可視情況地亦含少量促進劑（如鋇與錳），而且敘述於，例 如，.J.D· Stoupe 之”An X-Ray Diffraction Study of the Copper Chromites and of the “Copper-Chromium Oxide” Catalyst” J.Am.Che.Soc·，第 71 卷，1949，第 589 頁；A.Iimura 等人 之 ’’Catalysis by “Copper Chromites’’， I， The effect of hydrogen Reduction on the composition, structure and catalytic activity for methanol decomposition”，Bull. Chem. Soc. Jp·，56, 2203-2207 (1 993); R.B.C· Pillai 之”A Study of the pre-activation of a copper chromite catalyst’’，Catalysis 〇 Letters 26 (1 994) 365-371 ° 銅與鋁可以對應氧化物之形式含於用於本發明之觸媒組 成物。 依照以上指定，含鉻礦銅之觸媒組成物可含鋇及/或錳（ 較佳爲氧化物之形式）作爲促進劑。鋇或錳含量相對於組成 物總重量低於1 5重量％，而且較佳爲〇. 1至5重量％。鋇與 錳之重量百分比指其以元素表示之含量。 含於用於芳族化合物（特別是苯）之烷化方法之觸媒組成 201041650 物之固態酸材料較佳爲沸石本性，而且可含一或更多種沸石 材料。可使用之沸石爲沸石貝他、沸石Y、ZSM-12、與絲光 沸石。這些沸石敘述於”Altas of zeolite structure typrs”， CH, Baerolocher、W.M.Meier 與 D,H. Olson，2001，第 5 版 ，Elsevier。較佳態樣爲使用沸石貝他。 沸石係以酸形式使用，即，以氫離子或通常爲酸抗衡其中 . 所有源自存在於結構中之鋁之負電荷。 (四）實施方式 〇 作爲依照本發明方法之觸媒組成物成分之沸石貝他相當 於美國專利3,3 08，069所述者，而且爲具有以下組成物之多 孔性結晶材料 [(x/n) M (l±0.1-x) TEA] A10 2 · S i Ο 2 · wH 2 Ο 其中n爲M之氧化狀態，x小於1，y範圍爲5至100, w 範圍爲0至4，Μ爲選自週期表系統第ΙΑ、IIA、IIIA族或 過渡金屬之金屬，及TEA爲氫氧化四乙銨。 本發明之較佳態樣爲沸石貝他爲酸形式，即，其中H +離 〇子部份地或完全地取代起初存在之金屬陽離子之形式。 此取代係依照已知方法藉由交換銨離子，清洗繼而燒而 進行。 可用於本發明之烷化方法之觸媒組成物（包括固態酸材料 與銅）可包括適當之黏合劑，例如，第III A、IV A與IVB族 之氧化物。更佳爲，觸媒系統可含矽或鋁之氧化物作爲黏合 載劑。甚至更佳爲，觸媒系統可含-氧化鋁作爲黏合載劑。 -氧化鋁爲已知材料，而且以前驅體銶酸鹽或p -銶酸鹽 -10- .201041650 之形式商業可得’繼而在最終燒結相製備觸媒系統時轉變成 -氧化鋁。 黏合劑較佳爲以相對觸媒系統範圍爲5:95至95:5之重量 比相對量使用。 本發明之特佳態樣爲，使用含鉻礦銅與貝他型式沸石（酸 形式）之觸媒系統。此組成物可依照上述含無機黏合劑。 . 銅較佳爲以相對固態酸材料範圍爲0.001至10,更佳爲範 圍爲0·01至2之金屬重量比例，含於本發明之觸媒組成物 〇 中。在觸媒組成物含一或更多種選自第ΙΙΙΑ、IVA、ΙΙΙΒ、 IVB、VB、VIB、VIIB族、VIII族（限於鐵、釕與餓）、及 鑭系之元素時，各元素較佳爲相對固態酸材料範圍爲0.001 至10，更佳爲範圍爲0.01至2之金屬重量比例。 如上所述，用於本發明之觸媒系統含具烷化官能基之固態 酸成分、及含銅、視情況地及一或更多種選自第III A、IV A 、ΙΙΙΒ、IVB、VB、VIB、VIIB 族、VIII 族（限於鐵、釕與 餓）、及鑭系元素之元素之具氫化官能基之金屬成分。 〇 依照各種實際組合步驟，可由上述成分開始製備用於本發 明之觸媒系統，其含固態酸成分及含銅、視情況地及一或更 多種選自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、 VIII族（限於鐵、釕與餓）、及鑭系元素之元素之金屬成分 ，其各維持上列之指定特徵》 因此，本發明之觸媒系統可包括一或更多個各含單一官能 基之獨特區，此官能基氫化鍵聯至金屬成分或烷化鍵聯至酸 成分（特別是沸石），或具上述特徵之氫化與烷化官能基。 -11- .201041650 一些製備觸媒系統之步驟之實例表示於下且略示地示於 第1圖。 在此圖中，I指觸媒組成物之金屬成分，其含銅、及視情 況地一或更多種選自第 IIIA、IVA、IIIB、IVB、VB、VIB 、VIIB族、VIII族（限於鐵、釕與餓）、及鑭系元素之元 素，該成分具有氫化官能基。在金屬成分僅含銅時，其較佳 . 爲氧化物之形式。在金屬成分亦含選自第ΠΙΑ、IVA、IIIB 、IVB、VB、VIB、VIIB 族、VIII 族（限於鐵、釕與餓）、 〇 及鑭系之元素時，較佳爲其亦氧化物之形式。在此情形，例 如，成分可藉由機械混合氧化物而製備。在其中銅及選自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於 鐵、釕與餓）之元素爲混合氧化物之特定情形，例如，成分 I可依照已知之共沉澱技術，或藉由熔化存在於混合氧化物 之金屬氧化物而製備。金屬成分I較佳爲包括鉻礦銅。 再度參考第1圖，A指含烷化官能基之固態酸成分，較佳 爲沸石系。可使用之沸石較佳爲沸石貝他、沸石Y、ZSM-12 〇 、與絲光沸石。較佳態樣爲使用沸石貝他。固態酸成分（較 佳爲沸石系）可混合適當黏合劑（例如，第ΠΙΑ、IVA與IVB 族元素之氧化物）使用。固態酸成分A更佳爲含矽或鋁之氧 化物作爲黏合載劑。甚至更佳爲，固態酸成分A含-氧化 鋁作爲黏合載劑。具黏合劑之沸石組成物可依照任何已知技 術製備。在沸石貝他之情形，例如，其可如EP 687500與 EP 847802專利所述而製備。 再度參考第1圖，AI指含氫化與烷化官能基之組成物。 -12- 201041650 以AI表示之組成物亦可含適當之黏合劑，例如，第ΙΙΙΑ、 IVA與IVB族之氧化物。以ΑΙ表示之組成物更較佳爲含矽 或鋁之氧化物作爲黏合載劑。甚至更佳爲，組成物ΑΙ含-氧化鋁作爲黏合載劑。組成物ΑΙ可依照熟悉此技藝者已知 之任何技術製備，例如，a)浸漬，b)離子交換或c)擠壓，其 敘述於下= . a)例如，可藉由以含銅鹽、視情況地及選自第ΙΠΑ、IVA、 IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於鐵、釕與 〇 餓）、及鑭系元素之鹽之水溶液浸漬固態酸成分（較佳爲 沸石本性），乾燥且燒結所得產物而操作。可使用銅鹽及 第 IIIA、IVA、ΠΙΒ、IVB、VB、VIB、VIIB 族、VIII 族 (限於鐵、釕與餓）、及鑭系元素之鹽之分別溶液。以此 方法得到之產物可視情況地混合上述之適當黏合劑（例如 ，第III A、IV A與IVB族之氧化物）使用。或者，可藉由 以含銅鹽、視情況地及選自第IIIA、IVA、IIIB、IVB、 VB、VIB、VIIB族、VIII族（限於鐵、釕與餓）、及鑭 〇 系之鹽之水溶液之浸漬固態酸材料與黏合劑之混合物，乾 燥且燒結所得產物而操作。Accordingly, the object of the present invention relates to a process for alkylating an aromatic compound comprising reacting an aromatic compound with a ketone in the presence of a catalyst composition comprising a solid acid material and copper. Preferably, the catalyst composition also contains one or more selected from the group consisting of Groups IIIA, IVA, ΙΠΒ, IVB, VB, VIB, VIIB, VIII 201041650 (limited to iron, strontium and starvation), and lanthanides. The element of the element. In a particularly preferred aspect, the catalyst composition contains one or more elements selected from the group consisting of Group III A and Group VIB elements. The aromatic compound is preferably benzene. The ketone is preferably acetone. More particularly, 'the object of the invention relates to a method of producing cumene from benzene' which comprises reacting in the presence of a catalyst system comprising a solid acid material and copper. Acetone, benzene and hydrogen 'in a single step reaction. Preferably, the catalyst composition for alkylating benzene to cumene additionally contains one or more selected from Groups 0 IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, and VIII (limited to Iron, sputum and hungry), and elements of actinides. A particularly preferred aspect is that the catalyst composition contains one or more elements selected from the group consisting of elements of Groups II and VIB, preferably chromium or aluminum. The alkylation process for the purposes of the present invention is relatively simple to prepare phenol from cumene: in fact it is not necessary to first carry out the chemical reduction of acetone to isopropanol (for example, as described in U.S. Patent 5,1,60,497), followed by isopropyl The alcohol is chemically dehydrated and converted to isopropene (for example, as described in U.S. Patent No. 5,0,7,72,9), and finally, benzene is chemically converted to benzene by propylene (for example, as described in ΕΡ 439,032). It is usually carried out under slightly different reaction conditions for the reactions discussed and in the presence of different catalysts. The catalyst system used in the process of the present invention allows all of the chemical changes required to start the preparation of cumene from the reagents acetone, benzene and hydrogen in a single reaction step, maximizing the yield of cumene and allowing various reagents The secondary reaction between the intermediate and the product is minimized. -7- 201041650 It is expected that the total yield of the art can be expected to be a secondary and undesired reaction. The parallel reduction reaction of benzene with hydrogen into cyclohexene, cyclohexane and hexane, and the formation of acetone to 4- a parallel condensation reaction of methyl-3-penten-2-one, and subsequent reaction of these by-products with various reagents and products of the main reaction, for example, alkylation of benzene to phenylcyclohexane by cyclohexene, and Reduction of 4-methyl-3-penten-2-one to 4-methyl-2-pentanone and 4-methyl-2-pentanol due to hydrogen. Catalyst systems useful in the process of the present invention unexpectedly convert the reagents to the desired product to minimize the formation of undesirable products.触) A catalyst system for the alkylation process of aromatic compounds, particularly benzene, for the purposes of the present invention, comprising a solid acid material and copper, wherein the copper is preferably in the form of an oxide. According to a preferred embodiment, the catalyst composition also contains one or more selected from the group consisting of ΠΙΑ, IVA, ΙΙΙΒ, IVB, VB, VIB, VIIB, VIII (limited to iron, strontium and starvation), and lanthanides. The element. The elements of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, VIII (limited to iron, lanthanum and ammonium), and lanthanides are preferably also in the form of oxides. In particular, copper and these elements may be contained in the catalyst composition in the form of a mixed oxide. According to a particularly preferred aspect, the catalyst composition contains one or more elements selected from the group consisting of elements of Groups VI and VIB. According to the above designation, the elements of Groups III and VIB are preferably in the form of oxides. In particular, copper and these elements may be contained in the catalyst composition in the form of a mixed oxide. A particularly preferred aspect of the invention is the use of a catalyst composition comprising copper and an element selected from the group consisting of chromium and aluminum. In particular, copper and these elements may be included in the catalyst composition in the form of a mixed oxide. 201041650 In particular, copper and chromium may be included in the catalyst composition in the form of chrome ore. Chromium ore is represented by the experimental formula CuO_CuCr2〇4. CuCr2〇4 is known as C.A.S. R.N. 12018-10-9 and is described in "Gmelins Handbuch der Anorganischen Chemie, 8th edition, Vol. Kupfer, Part b, Installation 3, System number 60' page 60". In the process of the present invention, a commercially available material called chrome ore copper containing Cu (II) and Cr (III) having different ratios of CuO and CuCr 204 may be used. These materials are known to those skilled in the art and may optionally contain small amounts of promoters (e.g., barium and manganese) and are described, for example, in "JD. Stoupe". An X-Ray Diffraction Study of the Copper Chromites And of the "Copper-Chromium Oxide" Catalyst" J. Am. Che. Soc., Vol. 71, 1949, p. 589; A. Iimura et al.''Catalysis by "Copper Chromites', I, The effect Of hydrogen reduction on the composition, structure and catalytic activity for methanol decomposition", Bull. Chem. Soc. Jp., 56, 2203-2207 (1 993); RBC·Pillai" A Study of the pre-activation of a copper Chromite catalyst'', Catalysis 〇 Letters 26 (1 994) 365-371 ° Copper and aluminum may be contained in the form of oxides for the catalyst composition used in the present invention. According to the above specification, the composition of the chrome-containing copper catalyst The material may contain cerium and/or manganese (preferably in the form of an oxide) as a promoter. The cerium or manganese content is less than 15% by weight, and preferably from 0.1 to 5% by weight, based on the total weight of the composition.钡 and manganese The weight percentage refers to the content expressed by the element. The catalyst composition for the alkylation process for aromatic compounds (especially benzene) 201041650 is preferably zeolite in nature and may contain one or more Zeolite materials. The zeolites which can be used are zeolite beta, zeolite Y, ZSM-12, and mordenite. These zeolites are described in "Altas of zeolite structure typrs", CH, Baerolocher, WMMeier and D, H. Olson, 2001, Version 5, Elsevier. The preferred aspect is the use of zeolite beta. Zeolites are used in acid form, ie, with hydrogen ions or usually acid, all of which are derived from the negative charge of aluminum present in the structure. Embodiment 〇 Zeolite, which is a catalyst composition component according to the method of the present invention, is equivalent to that described in U.S. Patent No. 3,308,069, and is a porous crystalline material having the following composition [(x/n) M (l±0.1-x) TEA] A10 2 · S i Ο 2 · wH 2 Ο where n is the oxidation state of M, x is less than 1, y is in the range of 5 to 100, w is in the range of 0 to 4, and Μ is selected Gold from the periodic table system, group II, IIA, IIIA or transition metals , And TEA is tetraethylammonium hydroxide. A preferred aspect of the invention is that the zeolite beta is in the acid form, i.e., wherein H + is partially or completely substituted for the initially present metal cation. This substitution is carried out in accordance with a known method by exchanging ammonium ions, washing and then burning. The catalyst composition (including the solid acid material and copper) which can be used in the alkylation process of the present invention may comprise a suitable binder, for example, an oxide of Groups III A, IV A and IVB. More preferably, the catalyst system may contain an oxide of ruthenium or aluminum as a binder. Even more preferably, the catalyst system may contain alumina as the binder. - Alumina is a known material and is commercially available in the form of precursor bismuth citrate or p- phthalate -10-. 201041650, which in turn is converted to alumina in the final sintering phase preparation of the catalyst system. Preferably, the binder is used in a relative amount by weight relative to the catalyst system ranging from 5:95 to 95:5. A particularly preferred aspect of the invention is the use of a catalyst system comprising chrome ore and beta type zeolite (acid form). This composition can be used in accordance with the above-mentioned inorganic binder. The copper is preferably contained in the catalyst composition of the present invention in a proportion by weight of the metal in the range of from 0.001 to 10, more preferably from 0. 01 to 2, relative to the solid acid material. When the catalyst composition contains one or more elements selected from the group consisting of ΙΙΙΑ, IVA, ΙΙΙΒ, IVB, VB, VIB, VIIB, VIII (limited to iron, strontium and starvation), and lanthanides, each element is more Preferably, the relative solid acid material ranges from 0.001 to 10, more preferably from 0.01 to 2 metal by weight. As described above, the catalyst system for use in the present invention contains a solid acid component having an alkylating functional group, and containing copper, optionally, and one or more selected from the group consisting of III A, IV A, ΙΙΙΒ, IVB, VB. Metal components having hydrogenated functional groups of elements VIB, VIIB, VIII (limited to iron, strontium and starvation), and elements of actinides. 〇 In accordance with various practical combination steps, a catalyst system for use in the present invention may be prepared starting from the above ingredients, comprising a solid acid component and containing copper, optionally and one or more selected from the group consisting of IIIA, IVA, IIIB, IVB, Metal components of elements VB, VIB, VIIB, VIII (limited to iron, antimony and starvation), and elements of actinides, each of which maintains the specified characteristics listed above. Thus, the catalyst system of the present invention may comprise one or more A plurality of distinct regions each containing a single functional group that is hydrogenated to a metal component or alkylated to an acid component (particularly a zeolite), or a hydrogenation and alkylation functional group as described above. -11-.201041650 Some examples of the steps for preparing a catalyst system are shown below and are shown schematically in Figure 1. In the figure, I refers to the metal component of the catalyst composition, which contains copper, and optionally one or more selected from the group consisting of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, and VIII (limited to Iron, strontium and hungry), and elements of lanthanides, which have hydrogenated functional groups. When the metal component contains only copper, it is preferably in the form of an oxide. When the metal component also contains an element selected from the group consisting of ΠΙΑ, IVA, IIIB, IVB, VB, VIB, VIIB, VIII (limited to iron, strontium and starvation), lanthanum and lanthanide, it is preferably also an oxide form. In this case, for example, the ingredients can be prepared by mechanically mixing the oxides. In the specific case where copper and an element selected from the group consisting of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, Group VIII (limited to iron, strontium and starvation) are mixed oxides, for example, component I can be known according to known Coprecipitation techniques, or by melting metal oxides present in mixed oxides. The metal component I preferably includes chrome ore. Referring again to Figure 1, A refers to a solid acid component containing an alkylating functional group, preferably a zeolite system. The zeolite which can be used is preferably zeolite beta, zeolite Y, ZSM-12®, and mordenite. A preferred aspect is the use of zeolite beta. The solid acid component (preferably zeolite) may be mixed with a suitable binder (e.g., oxides of Group I, IVA and IVB elements). The solid acid component A is more preferably an oxide containing ruthenium or aluminum as a binder carrier. Even more preferably, the solid acid component A contains aluminum oxide as a binding carrier. The zeolite composition with a binder can be prepared according to any known technique. In the case of zeolite beta, for example, it can be prepared as described in EP 687500 and EP 847802 patents. Referring again to Figure 1, AI refers to a composition containing hydrogenated and alkylated functional groups. -12- 201041650 The composition represented by AI may also contain suitable binders, for example, oxides of Groups I, IVA and IVB. The composition represented by ruthenium is more preferably an oxide containing ruthenium or aluminum as a binder carrier. Even more preferably, the composition contains - alumina as a binder carrier. The composition can be prepared according to any technique known to those skilled in the art, for example, a) impregnation, b) ion exchange or c) extrusion, which is described below. a) For example, by using a copper salt, And an aqueous solution of a solid acid component (preferably a zeolite) impregnated with an aqueous solution selected from the group consisting of salts of Groups I, IVA, IIIB, IVB, VB, VIB, VIIB, Group VIII (limited to iron, strontium and starvation), and lanthanides Intrinsic), drying and sintering the resulting product to operate. A separate solution of a copper salt and salts of Groups IIIA, IVA, ΠΙΒ, IVB, VB, VIB, VIIB, VIII (limited to iron, strontium and starvation), and lanthanides can be used. The product obtained in this way can optionally be used by mixing the above suitable binders (e.g., oxides of Groups III A, IV A and IVB). Alternatively, by using a copper-containing salt, optionally, and selected from the group consisting of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, Group VIII (limited to iron, strontium and starvation), and salts of lanthanides The aqueous solution is impregnated with a mixture of the solid acid material and the binder, dried and sintered to operate.
b)在離子交換在使用離子交換技術時，例如，將固態酸材料 (較佳爲沸石本性）置於含銅鹽、及視情況地選自第III A 、IVA、IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於 鐵、釕與餓）、及鑭系之鹽之水溶液中，而且將混合物攪 拌數小時。藉過濾回收懸浮液中之固體，以去礦質水清洗 及乾燥：得到具銅離子、可能及選自第IIIA、IVA、IIIB -13- 201041650 、IVB、VB、VIB、VIIB族、VIII族（限於鐵、釕與餓） 、及鑭系金屬之離子之交換形式之固態酸材料。以此方式 得到之材料可視情況地混合上述之適當黏合劑使用。或者 ，使用固態酸材料與適當黏合劑之組成物，其接受上述之 離子交換法。 c)或者，可使用擠壓法，其中以任何傳統方法將兩種成分（ 即，固態酸材料（較佳爲沸石系）與金屬成分）之機械混 合物漿料混合粒化酸溶液，擠壓，乾燥，及燒結。以此方 〇 式得到之產物可視情況地混合以上定義之適當黏合劑。或 者，將這些成分（即，固態酸材料（較佳爲沸石系）、金 屬成分與以上定義之適當黏合劑）之機械混合物接受擠壓 法。依照以上指定，例如（第la圖），觸媒系統可僅包 括含金屬與酸成分之AI組成物區，其具有烷化及氫化官 能基》 依照另一個具體實施例中，例如（第lb圖），觸媒系統 可包括二或更多個各含酸與金屬成分之分離AI組成物區， 〇 其具有烷化及氫化官能基，其中單區之組成物係化學本性及 烷化與氫化官能基間之比例不同。AI組成物區之各單區係 以上述已知方法之一製備，然後在反應器內部藉層化將區組 合。 觸媒系統之另一種製備步驟（第lc圖）包括，例如，二 或更多個獨特區，其一有僅含催化氫化官能基之金屬成分I ，而在其餘之區有一或更多種組成物AI，其具有不同組合 之兩種成分（具烷化與氫化官能基）。含兩種官能基之組成 -14- 201041650 物AI之各單區係以上述已知方法之一製備。 在另一個具體實施例（第Id圖）中，觸媒系統包括，例 如，二或更多個獨特區，其一有僅含催化氫化官能基之金屬 成分I，而在後續之區有具有烷化催化官能基之成分A。酸 成分A (較佳爲沸石系）可混合上述之適當黏合劑使用。 在進一步具體實施例（第le圖）中，觸媒系統包括，例 如，單區，其中配置機械地彼此混合之觸媒組成物之兩種成 分（各爲I與A)。在此情形，固態酸成分A (較佳爲沸石 〇 系）亦可混合上述之適當黏合劑使用。 在另一個具體實施例（第If圖）中，觸媒系統^括，例 如，二或更多個獨特區，其一有僅含催化氫化官能基之觸媒 系統成分I，而在其餘之區有一或更多對機械地混合之不同 成分I與A，其各僅含催化氫化官能基或僅含催化烷化官能 基。在此情形，固態酸成分A (較佳爲沸石系）亦可混合上 述之適當黏合劑使用。 在觸媒系統具有僅含催化氫化官能基之金屬成分I之區時 〇 ，較佳爲其係最先接觸試劑流（特別是苯、丙酮與氫）者。 此外，基於所述步驟，如果需要，顯然熟悉此技藝者易於製 造特徵爲同時存在氫化官能基（其活性梯度沿一個方向降低 )及烷化官能基（其活性梯度沿相反方向降低）之觸媒系統 〇 氫化官能基之活性梯度較佳爲隨試劑（特別是苯、丙酮與 氫）之進料方向與流動而降低，而烷化官能基之活性梯度隨 相反方向與流動而降低。 -15- 201041650 依照本發明烷化方法之較佳態樣，較佳爲在通常範圍爲50 至350°C，較佳爲100至25 0°C之反應溫度操作。壓力通常等 於或高於大氣壓力，而且較佳爲範圍爲1至50巴。進料使 用不小於1而且較佳爲大於2之芳族烴與酮間（特別是苯與 丙酮間）之莫耳比例。進料使用不小於1而且較佳爲大於2 之氫與酮（特別是丙酮）間之莫耳比例。觸媒組成物較佳爲 在氫流中預先活化。 反應可在含一或更多個觸媒床之固定床觸媒反應器中方 〇 便地進行。在此情形，可將全部試劑以所需比例進料至反應 器之第一觸媒床，或將試劑或其中某些部份地進料至不同觸 媒床。 然而，一些以上述方法製備之組成物亦可方便地用於非固 定床反應器之反應器。 參考第2圖，依照在此申請之方法及依照本發明之具體實 施例，苯、丙酮與氫係在所述觸媒系統存在下及在得到反應 產物（其主要含異丙基苯、未轉化苯、未轉化氣、水、與聚 〇 異丙基苯）之所示條件下，在單一步驟中反應。 反應產物係使用習知分離方法在分餾部份S分餾，如脫氣 、蒸餾或液體分離，而得到主要含氫之第一部份、主要含水 之第二部份、主要含苯之第三部份、主要含異丙基苯之第四 部份、及主要含聚異丙基苯之第五部份。 第一部份（含氫）隨丙酮與苯再用於反應步驟，自方法將 第二部份（含水）移除’第三部份（含苯）部份地隨丙酮與 氫再用於反應步驟且部份地用於後續反應步驟（稱爲轉烷化 -16- 201041650 步驟），其中其與第五部份（含聚異丙基苯）反應而再度製 造所需之異丙基苯。 轉烷化爲當代技藝已知之反應，而且係在固態酸觸媒存在 下’較佳爲在沸石爲主固態酸觸媒存在下，更佳爲在貝他型 沸石爲主固態酸觸媒（例如，EP 687500與EP 847802專利 所述）存在下進行。 亦如EP 6 8 75 00與EP 847 8 02專利所述，轉烷化反應之溫 度條件係選自100至3 5 0°C，壓力選自10至50 atm，及WHSV 〇 範圍爲0.1至200小時-1。 轉烷化反應產物係使用與分離部份相同之習知分離方法 分飽。 因此’來自分離部份之第三部份含來自烷化步驟與轉烷化 步驟之未轉化苯。來自分離部份之第四部份含來自烷化步驟 與轉烷化步驟之異丙苯，及來自分離部份之第五部份含來自 烷化步驟與轉烷化步驟之聚異丙基苯。 依照此方法（本發明之目的）得到之異丙苯可藉由氧化成 〇 氫氧化異丙苯，繼而將氫氧化物重組成酚與丙酮，而用於製 造酚。 因此，本發明之進一步目的係關於一種製造酚之方法，其 包括以下之步驟： (a) 在包括固態酸材料與銅之觸媒系統存在下，反應苯、丙 酮與氫， (b) 將異丙苯氧化成氫過氧化異丙苯， (c) 將氫過氧化異丙苯重組成爲酚與丙酮。 -17- 201041650 在步驟（C)中形成之丙酮可再循環至異丙苯合成步驟（a)。 用於步驟（a)之觸媒組成物較佳爲亦含一或更多種選自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、VIII 族（限於 鐵、釕與餓）、及鑭系元素之元素。特佳態樣爲，觸媒組成 物含一或更多種選自第ΠΙΑ與VIB族元素之元素，而且依 照以上關於本發明之烷化方法所指定。使用之觸媒組成物較 佳爲含沸石貝他、鉻礦銅、視情況地及無機黏合劑。 將異丙苯氧化成爲氫過氧化異丙苯、將氫過氧化異丙苯重 〇 組成爲酚與丙酮、及將酚純化之各種途徑在文獻中爲已知的 ，例如，如美國專利5，160,497與美國專利5,01 7,729所述 〇 異丙苯成爲氫過氧化異丙苯之氧化步驟可藉由，例如，在 範圍爲60至150°C之溫度及在範圍爲1至1〇公斤-f/平方公 分之壓力以分子氧進行。較佳爲其在引發劑與控制pH用鹼 化合物存在下操作。 氫過氧化異丙苯成爲酚與丙酮之轉變步驟係在，例如，強 〇 酸（如硫酸），或例如，交換樹脂或矽一氧化鋁存在下進行 。結束時，將反應混合物濃縮以回收丙酮’然後將其再循環 至烷化步驟（a)。可明確地見到，如何進行藉由將丙酮再循環 至步驟（a)進行由氫、氧與苯開始製造酚而僅共同製造水之方 法。 依照較佳態樣，在第一步驟結束時’在藉分餾分離所需產 物異丙苯（將其傳送至後續氧化步驟）後’其餘部份之聚異 丙基苯與苯用於轉烷化反應之分離步驟而回收其他之異丙 -18- 201041650 苯。 轉烷化反應係在沸石貝他或以沸石貝他爲主之觸媒存在 下進行，特別是依照EP 687500與EP 847802專利所述而製 備者，其亦敘述反應條件。 含酸形式沸石（較佳爲沸石貝他）、銅及視情況地一或更 多種選自第 IIIA、IVA、IIIB、IVB、VB、VIB、VIIB 族、 VIII族（限於鐵、釕與餓）、及鑭系元素之元素之本發明觸 媒組成物爲新穎的，而且爲本發明之進一步態樣。 〇 此觸媒組成物較佳爲含沸石貝他、銅、及選自鉻與鋁之元 素。此組成物所含之金屬較佳爲氧化物之形式。依照本發明 之特定態樣，含鉻礦銅形式之銅與鉻。 銅較佳爲以相對沸石範圍爲0.001至10，更佳爲範圍爲 0.01至2之金屬重量比例，含於本發明之觸媒組成物中。在 觸媒組成物含一或更多種選自第IIIA、IVA、IIIB、IVB、 VB、VIB、VIIB族、VIII族（限於鐵、釕與餓）、及鑭系之 元素時，各元素較佳爲相對沸石範圍爲0.001至10,更佳爲 Ο 〇.〇1至2之金屬重量比例。在用於此專利之觸媒組成物之金 屬成分包括鉻礦銅時，可存在鋇與錳作爲促進劑。這些觸媒 組成物可另外含黏合劑》這些觸媒組成物之製備係依照所有 上述之方法。 茲提供以下之實例以進一步描述本發明而絕非限制其範 圍。 管例1-觸媒系統之製備 製備觸媒系統，其包括10克具有以下組成物（以元素之 -19- 201041650 重量％表示）之鉻礦銅爲主觸媒（SiidChemie製造，商標名 G99b):銅 35%、鉻 31%、鋇 2%、錳 2.5%，以下以「 材料A1」表示，及4.5克以依照EP 6 8 7500專利實例1所述 之指示製備之沸石貝他爲主之觸媒，稱爲「材料B1」。用 於製備材料B1之沸石貝他爲Zeoly st公司之產品，商標名 CP-806 BL 25。 製備觸媒系統使得該系統之第一區僅包括等於3克之量之 材料A1，及第二區包括等於7克材料A1與4.5克材料B1 〇 之量之材料A1與B1之機械混合物。因此，如此製備之觸媒 系統之總量等於14.5克。 复J例2-觸媒系統之製備 由已用於以上實例之材料G-9 9b (57克）與沸石貝他（80 克）’及Laroche公司以商標名Versal 450上市之氧化鋁p-銶酸鹽（143克）開始製備觸媒系統。 材料在犁鏟混合器中機械地混合約25分鐘，然後不中斷 混合，將1 7 5 cc之5 % w/w乙酸水溶液加入如此得到之粉末 〇 ^ 混合物，再混合約20分鐘。 然後使用HUTT型齒輪壓縮擠壓器使如此得到之中間物接 受擠壓，如此得到之產物繼而接受老化不少於約48小時之 時間。 在老化期間後，粒狀形式之產物然後在550。(：溫度之空氣 中接受燒結處理約5小時，得到稱爲「材料B2」之材料， 其含約25%材料G99b、約30%沸石貝他、與約45%氧化銘 黏合載劑。 -20- 201041650 製備包括其中爲材料B2之單區之觸媒系統。如此製備之 觸媒系統總量等於9.0克。 實例3-觸媒系統之製備 製備包括兩個獨特區之觸媒系統，第一區含3克已用於 實例1之材料A1’及第二區含8克依照實例2所述之步 驟製備之材料B2。因此，觸媒系統之總量等於丨丨克。 實例4-觸媒系統之製備 將37克依照EP 6 87500專利實例1提供之指示製備之沸 Q 石貝他爲主觸媒（12_16篩目）裝入具有500毫升體積之旋 蒸器燒瓶中，然後在室溫真空乾燥2小時。 製備包括 30.34克去礦質水與 8.0克硝酸銅 Cu(N03)2.2.5H20 ( MW = 23 2.59，34.4 毫莫耳）之溶液。固 體係在室溫在真空下浸漬。使其在真空下緩慢地轉動3小時 。然後在120°C烤箱中乾燥2小時。其以i°C分鐘-1之增加速 率在 3 16°C/4小時燒結。 將18.8克產物進行二次浸漬，其如前但使用包括4.06克 〇 硝酸銅 Cu(N03)2,2.5H20( MW = 232.59, 1 7.5 毫莫耳）與 15.42 克去礦質水之溶液，在31 6°C燒結。 固體係在室溫在真空下浸漬。使其在真空下緩慢地轉動3 小時。其在1 2 0 °C烤箱中乾燥2小時，而且以1 °C分鐘· 1之增 加速率在482°C/8小時燒。 回收19.4克燒結產物（10.29%銅）。 實例5-觸媒測試 使用下述之實驗裝置進行觸媒測試。 -21 - 201041650 實驗裝置包括試劑苯與丙酮之槽、試劑苹與丙酮之進料栗 、用於來自氣瓶之氫之流速控制之質量計、在試劑進入反應 前之靜態混合器、試劑預熱單位、位於電熱烤箱內部之鋼反 應器（烤箱內及反應器內裝有溫度調節）、反應器內部之壓 力調節系統（藉空氣閥）、反應溶離液之冷卻器、及液態與 氣態產物之收集系統。 位於電熱烤箱內部之反應器包括鋼氣瓶管線，其具有機械 密封系統且內徑等於約2公分。 〇 沿反應器主軸有直徑等於1毫米之溫度阱，其含可沿反應 器主軸因此沿觸媒床主軸自由地移動之熱偶。 將如實例1所述而製備之觸媒系統（大小範圍爲1至2毫 米）以等於14.5克之量裝入反應器中，使觸媒床總高度等 於8.5公分。 將定量惰性石英材料以觸媒床上方等於2公分及下之方2 公分高度，裝在觸媒床上下。 然後使觸媒以反應器內部之溫度等於160°C在氮流中乾燥 〇 1小時，繼而將5.2毫升/分鐘之低壓氫流進料60分鐘，繼 而在180 °C將15.8毫升/分鐘之氫流進料120分鐘，最後在 200°C將23.6毫升/分鐘之氫流進料180分鐘，然後中止氫進 料及使反應器之溫度回到等於150°C之値，實驗裝置持續地 保持在氮流中。 —但達到150°C固定溫度，將氮流中止且以等於0.245毫 升/分鐘之流速啓動苯進料。 此系統在這些條件下維持60分鐘，然後再啓動流速等於 -22- 201041650 27.3毫升/分鐘之氫進料，數分鐘後啓動流速等於0.012毫升 /分鐘之丙酮進料。 在丙酮進料後約3小時，移除液態與氣態部份之反應溶離 液樣品，繼而藉氣相層析術分析。 表1歸納操作條件及所得之結果。在此表中： - WHSV表示苯與丙酮（不含氫）之小時流速總和及觸媒 系統量之間之比例； 一[芳基]/[丙酮]選擇性表示轉化成異丙苯+聚異丙基苯（ 〇 可轉烷化製造異丙苯之產物）之丙酮相對轉化丙酮總量之比 例； -[異丙苯]/[丙酮]選擇性表示轉化成異丙苯之丙酮相對 .轉化丙酮總量之比例； -[芳基]/[苯]選擇性表示轉化成異丙苯+聚異丙基苯之 丙酮相對轉化苯總量之比例。 實例6-觸媒測試 使用如實例5之相同實驗裝置及相同實驗條件進行觸媒測 Ο 試，但是裝以其量等於9克之依照實例2所述而製備之觸媒 系統，觸媒床總高度等於8.3公分。苯係以等於0.184毫升/ 分鐘之流速進料。 在丙酮進料開始後約3小時，移除液態與氣態部份之反應 溶離液樣品，繼而藉氣相層析術分析。 表1歸納操作條件及所得之結果。 實例7-觸媒測試 使用如實例5之相同實驗裝置及相同實驗條件進行觸媒測 -23- 201041650 試，但是裝以其量等於11克之依照實例3所述而製備之觸 媒系統，觸媒床總高度等於8.5公分。苯係以等於〇.251毫 升/分鐘之流速進料。 在丙酮進料開始後約3小時，移除液態與氣態部份之反應 溶離液樣品，繼而藉氣相層析術分析。 表1歸納操作條件及所得之結果。 實例8-觸媒測試 使用如實例5之相同實驗裝置及相同實驗條件進行觸媒測 〇 試，但是裝以其量等於11克之依照實例3所述而製備之觸 媒系統，觸媒床總高度等於8.5公分。丙酮係以等於0.009 毫升/分鐘之流速進料，苯係以等於0_072毫升/分鐘之流速 進料。 在丙酮進料開始後約3小時，移除液態與氣態部份之反應 溶離液樣品，繼而藉氣相層析術分析。 表1歸納操作條件及所得之結果。 實例9-觸媒測試 〇 使用如實例5之相同實驗裝置及相同實驗條件進行觸媒測 試，但是裝以其量等於5克之依照實例4所述而製備之觸媒 系統，觸媒床總高度等於5公分。 然後使觸媒在氮流中乾燥，及在約2小時內使反應器內部 之溫度由120°C升至190°C。一但達到190°C固定溫度，將氮 流中止且以等於0.2 54毫升/分鐘之流速啓動苯進料。此系統 在這些條件下維持60分鐘，然後再啓動流速等於27.3毫升 /分鐘之氫進料，數分鐘後啓動流速等於0.036毫升/分鐘之 -24- 201041650 丙酮進料。 在丙酮進料後約3小時，移除液態與氣態部份之反應溶 離液樣品，繼而藉氣相層析術分析。表1歸納操作條件 及所得之結果。 表1 實例號碼 5 6 7 8 9 觸媒系銃之量 （如 14.5 9 11 11 5 反應溫度 （°c) 150 150 150 150 190 反應壓力 （kpa) 100 100 100 100 100 總 WHSV(1T1) 0.9 1.1 1.2 0.4 3.0 [苯y[丙酮1莫耳比例 16.8 12.6 17.2 6.3 5.8 的]/【丙酮]莫耳埃例 7.4 7.4 7.4 9,77 2.5 丙酮轉化率 % 100.0 100 100 100 98,5 【芳基y[丙酮1遝擇性 % 96.6 88.3 94.6 980 89%1 [異丙苯】/[丙酮】選擇性 % 81.9 70.2 79.8 79.7 81.0 [芳基Η苯】選擇性％ 99.4 96.7 99.0 99.8 96.7 實例10-觸媒系統之製備 製備一種材料，其包括鋁酸銅爲主觸媒（Siidchemie製造 ’商標名期9,以下以「材料A2j表示，其具有以下之組 成物（以元素之重量％表示）：_ 39.3%、鋁ΐ5·5%、鋅 6.0%、錳 6.8% )、沸石貝他與氧化銘 與氧化鋁爲用於以上實例之相同材料。 將173克氧化鋁、192克沸石貝他、 P-銶酸鹽。沸石貝他 鏟混合器中且機械地混合約 124克T4489裝入犁 分鐘 然後不中斷混合，將 -25- 201041650 400 cc之2% w/w乙酸水溶液加入如此得到之粉末混合物， 再混合約60分鐘。 然後使用HUTT型齒輪壓縮擠壓器使如此得到之中間物接 受擠壓，得到之產物繼而接受老化不少於約48小時之時間 〇 在老化期間後，粒狀形式之產物繼而在約550。(：溫度之空 氣中接受燒結處理5小時，得到稱爲「材料B3」之材料， 其含約30%鋁酸銅T4489、約40%沸石貝他、與約30%氧化 〇 鋁黏合載劑。製備觸媒系統使得其包括兩個獨特區，第一區 含3克材料A2，及第二區含7克如所述而製備之材料B3。 因此，觸媒系統之總量等於10克。 實例1 1-觸媒系統之製備 製備包括已用於以上實例之鋁酸銅T4489與沸石貝他之 材料。 將298克沸石貝他、255克T4489裝入犁鏟混合器中且機 械地混合約60分鐘，然後不中斷混合，將3 65 cc之5% w/w 〇 乙酸水溶液加入如此得到之粉末混合物，再混合約20分鐘 〇 然後使用HUTT型齒輪壓縮擠壓器使如此得到之中間物接 受擠壓’得到之產物繼而接受老化不少於約48小時之時間 〇 在老化期間後，粒狀形式之產物繼而在約550。(：溫度之空 氣中接受燒結處理5小時，得到稱爲「材料B4」之材料， 其含約50%鋁酸銅T4489及約50%沸石貝他。製備觸媒系統 -26- 201041650 使得其包括兩個獨特區，第一區含3克材料A2，及第二區 含7克如所述而製備之材料B4。因此，觸媒系統之總量等 於10克。 實例12-觸媒測試 使用如實例5之相同實驗裝置進行觸媒測試。 將如實例10所述而製備之觸媒系統（大小範圍爲1至2 毫米）以等於10克之量裝入反應器中，使觸媒床總高度等 於8.5公分。 〇 將定量惰性石英材料以觸媒床上方等於2公分及下之方2 公分高度，裝在觸媒床上下。 然後使觸媒在氮流中乾燥1小時，此時將內溫升至210°C 。一但達到此溫度，將1.3毫升/分鐘之苯流進料約30分鐘 。然後使溫度降至194 °C，使壓力升至2100 Kpa，及中止氮 流。繼而將367毫升/分鐘之氫進料約30分鐘。最後中止苯 進料，及將0.77克/分鐘之苯與丙酮溶液[C6]/[C3] = 6.3流動 進料。 ^ 在丙酮進料開始後約3小時，自反應取出液態與氣態部份 之溶離液樣品，繼而藉氣相層析術分析。在進料開始後約24 小時，以相同之分析步驟重複取樣操作。 表2歸納操作條件及所得之結果。 實例13-觸媒測試 使用如實例5所述之相同實驗裝置及在如實例1 2之相同 實驗條件下進行觸媒測試。將如實例1 1所述而製備之觸媒 系統（大小範圍爲1至2毫米）以等於10克之量裝入反應 -27- 201041650 器中，觸媒床總高度等於8.1公分。 在丙酮進料開始後約3小時，自反應取出液態與氣態部份 之溶離液樣品，繼而藉氣相層析術分析。在進料開始後約24 小時，以相同之分析步驟重複取樣操作。 表2歸納操作條件及所得之結果。 實例14-觸媒測試 使用如實例5所述之相同實驗裝置及在如實例1 2之相同 實驗條件下進行觸媒測試，但是裝以其量等於1 1克之如實 〇 例3所述而製備之觸媒系統，觸媒床總高度等於8.3公分。 將0.76克/分鐘之苯與丙酮溶液[C6]/[C3] = 6.3流動進料。 在丙酮進料開始後約3小時，自反應取出液態與氣態部份 之溶離液樣品，繼而藉氣相層析術分析。在進料開始後約24 、1 73與3 84小時，以相同之分析步驟重複取樣操作。 表2歸納操作條件及所得之結果。 眚例15-觸媒測試 使用如實例5所述之相同實驗裝置進行觸媒測試，但是裝 Ο 以其量等於11克之如實例3所述而製備之觸媒系統，觸媒 床總高度等於8.4公分。 使觸媒以反應器內部之溫度等於160°C在氮流中乾燥1小 時，然後在低壓將5.2毫升/分鐘之氫流進料60分鐘，繼而 在180°C將15_8毫升/分鐘之氫流進料120分鐘，最後在200°C 將23.6毫升/分鐘之氫流進料180分鐘。然後中止氫進料及 使反應器之溫度回到等於170 °C之値，實驗裝置保持在氮流 中〇 -28- 201041650 —但達到170 °C固定溫度，將氮流中止且以等於0.36毫升 /分鐘之流速啓動苯進料。將壓力升至850 Kpa。 將系統維持在這些條件下60分鐘，然後以等於338毫升/ 分鐘之流速啓動氫進料；數分鐘後中止苯進料，及將0.76 克/分鐘之苯與丙酮溶液[C6]/[C3] = 6.3流動進料。 在丙酮進料開始後約3小時，自反應取出液態與氣態部份 之溶離液樣品，繼而藉氣相層析術分析。 表2歸納操作條件及所得之結果。 〇 實例16-觸媒測試 使用如實例5所述之相同實驗裝置進行觸媒測試，但是裝 以其量等於11克之如實例3所述而製備之觸媒系統，觸媒 床總高度等於8.4公分。 使觸媒在氮流中乾燥1小時，此時將反應器內部之溫度升 爲23(TC。一但達到此溫度，將1.3毫升/分鐘之苯流進料約 30分鐘。然後使溫度降至210°C，使壓力升至2900 Kpa，中 止氮流，及將3 67毫升/分鐘之氫流進料約30分鐘。最後中 Ο 止苯進料，及將0.76克/分鐘之苯與丙酮溶液[C6]/[C3] = 6.3 流動進料。 在丙酮進料開始後約20小時，自反應取出液態與氣態部 份之溶離液樣品，繼而藉氣相層析術分析。 表2歸納操作條件及所得之結果。 (五）圖式簡單說明 第1圖觸媒系統製備之實例（la〜If) 其中1指觸媒組成物之金屬成分； -29- 201041650 A接烷化官能基之固態酸成分； AI指含氫化與烷化官能基之組成物 第2圖本發明製得產物之方法流程b) In the case of ion exchange, when using an ion exchange technique, for example, a solid acid material (preferably zeolite in nature) is placed in a copper-containing salt, and optionally selected from the group consisting of III A, IVA, IIIB, IVB, VB, VIB. In the aqueous solution of the VIIB, VIII (limited to iron, strontium and starvation), and lanthanide salts, and the mixture is stirred for several hours. The solid in the suspension is recovered by filtration, washed and dried with demineralized water: obtained with copper ions, possibly and selected from the group consisting of IIIA, IVA, IIIB -13 - 201041650, IVB, VB, VIB, VIIB, VIII (limited to Solid acid materials in the form of exchange of iron, antimony and starvation, and ions of lanthanide metals. The material obtained in this manner can optionally be mixed with the above-mentioned suitable binder. Alternatively, a solid acid material and a composition of a suitable binder are used which accept the ion exchange method described above. c) Alternatively, an extrusion method may be employed in which a mechanical mixture slurry of two components (i.e., a solid acid material (preferably a zeolite system) and a metal component) is mixed with a granulated acid solution, extruded, by any conventional method. Dry, and sintered. The product obtained in this way can optionally be mixed with the appropriate binder as defined above. Alternatively, a mechanical mixture of these components (i.e., a solid acid material (preferably a zeolite system), a metal component, and a suitable binder as defined above) is subjected to extrusion. According to the above designation, for example (Fig. 1a), the catalyst system may comprise only an AI composition region containing a metal and an acid component having an alkylating and hydrogenating functional group, according to another embodiment, for example (Fig. lb) The catalyst system may comprise two or more separate AI composition regions each containing an acid and a metal component, which have alkylation and hydrogenation functional groups, wherein the composition of the single region is chemically and alkylated and hydrogenated. The ratio between the bases is different. Each single zone of the AI composition zone is prepared by one of the above known methods, and then the zones are combined by stratification inside the reactor. Another preparation step (Fig. lc) of the catalyst system comprises, for example, two or more distinct regions, one having a metal component I containing only catalytic hydrogenation functional groups and one or more constituents in the remaining regions. AI, which has two components in different combinations (with alkylation and hydrogenation functional groups). Compositions containing two functional groups -14- 201041650 Each single unit of the AI is prepared in one of the above known methods. In another embodiment (Fig. Id), the catalyst system comprises, for example, two or more distinct regions, one having a metal component I containing only a catalytic hydrogenation functional group and having an alkane in a subsequent region Component A of the catalytic functional group. The acid component A (preferably a zeolite system) may be used in combination with a suitable binder as described above. In a further embodiment (Fig. 3), the catalyst system comprises, for example, a single zone in which two components (I and A, respectively) of the catalyst composition mechanically mixed with each other are disposed. In this case, the solid acid component A (preferably a zeolite system) may also be used in combination with the above-mentioned suitable binder. In another embodiment (Fig. If), the catalyst system includes, for example, two or more distinct regions, one having a catalytic system component I containing only catalytic hydrogenation functional groups, and in the remaining regions There are one or more pairs of mechanically mixed different components I and A, each of which contains only a catalytic hydrogenation functional group or only a catalytic alkylation functional group. In this case, the solid acid component A (preferably a zeolite system) may also be used in combination with the above-mentioned suitable binder. In the case where the catalyst system has a region of the metal component I containing only the catalytic hydrogenation functional group, it is preferably the first to contact the reagent stream (especially benzene, acetone and hydrogen). Further, based on the steps, it is apparent to those skilled in the art that it is easy to produce a catalyst characterized by the simultaneous presence of a hydrogenation functional group whose activity gradient decreases in one direction and an alkylation functional group whose activity gradient decreases in the opposite direction, if necessary. The activity gradient of the system hydrazine functional group preferably decreases with the feed direction and flow of the reagents (especially benzene, acetone and hydrogen), while the activity gradient of the alkylation functional group decreases with the opposite direction and flow. -15- 201041650 In accordance with a preferred embodiment of the alkylation process of the present invention, it is preferred to operate at a reaction temperature typically in the range of from 50 to 350 ° C, preferably from 100 to 250 ° C. The pressure is usually equal to or higher than atmospheric pressure, and is preferably in the range of 1 to 50 bar. The feed uses a molar ratio of aromatic hydrocarbon to ketone (especially between benzene and acetone) of not less than 1 and preferably more than 2. The feed uses a molar ratio between hydrogen and ketone (especially acetone) of not less than 1 and preferably more than 2. Preferably, the catalyst composition is preactivated in the hydrogen stream. The reaction can be carried out conveniently in a fixed bed catalyst reactor containing one or more catalyst beds. In this case, all reagents may be fed to the first catalyst bed of the reactor in the desired ratio, or the reagents or portions thereof may be fed to different catalyst beds. However, some of the compositions prepared by the above methods can also be conveniently used in reactors for non-fixed bed reactors. Referring to Figure 2, in accordance with the methods of the present application and in accordance with specific embodiments of the present invention, benzene, acetone and hydrogen are present in the presence of the catalyst system and in obtaining a reaction product (which is predominantly cumene, unconverted The reaction is carried out in a single step under the conditions indicated for benzene, unconverted gas, water, and polyisopropylbenzene. The reaction product is fractionated in a fractionation section S by a conventional separation method, such as degassing, distillation or liquid separation, to obtain a first portion mainly containing hydrogen, a second portion mainly containing water, and a third portion mainly containing benzene. Part, mainly containing the fourth part of cumene, and the fifth part containing mainly isopropylbenzene. The first part (hydrogen) is reused in the reaction step with acetone and benzene. The second part (aqueous) is removed from the method. The third part (containing benzene) is partially regenerated with acetone and hydrogen. The step is used in part for the subsequent reaction step (referred to as the transalkylation-16-201041650 step) in which it is reacted with the fifth portion (containing polyisopropylbenzene) to reproduce the desired cumene. Transalkylation is a reaction known to the art of the art and is preferably in the presence of a solid acid catalyst, preferably in the presence of a zeolite-based solid acid catalyst, more preferably in a beta-based zeolite-based solid acid catalyst (eg Executed in the presence of EP 687500 and EP 847802. Also as described in EP 6 8 75 00 and EP 847 8 02, the temperature conditions for the transalkylation reaction are selected from 100 to 350 ° C, the pressure is selected from 10 to 50 atm, and the WHSV 〇 ranges from 0.1 to 200. Hour -1. The transalkylation reaction product is saturated using a conventional separation method which is the same as the separation portion. Thus the third portion from the separated portion contains unconverted benzene from the alkylation step and the transalkylation step. The fourth portion from the separated portion contains cumene from the alkylation step and the transalkylation step, and the fifth portion from the separated portion contains polyisopropylbenzene from the alkylation step and the transalkylation step . The cumene obtained according to this method (the object of the present invention) can be used for the production of phenol by oxidation to cumene hydrazine hydroxide, followed by reconstitution of the hydroxide to phenol and acetone. Accordingly, a further object of the present invention is directed to a method of making a phenol comprising the steps of: (a) reacting benzene, acetone and hydrogen in the presence of a catalyst system comprising a solid acid material and copper, (b) The propylbenzene is oxidized to cumene hydroperoxide, (c) the cumene hydroperoxide is recombined into phenol and acetone. -17- 201041650 The acetone formed in the step (C) can be recycled to the cumene synthesis step (a). Preferably, the catalyst composition used in the step (a) also contains one or more selected from the group consisting of Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, Group VIII (limited to iron, strontium and starvation), And elements of actinides. In a particularly preferred aspect, the catalyst composition contains one or more elements selected from the group consisting of elements of Groups II and VIB, and is as specified above in connection with the alkylation process of the present invention. The catalyst composition used is preferably zeolite beta, chrome ore, optionally, and inorganic binders. Various routes for the oxidation of cumene to cumene hydroperoxide, the formation of cumene hydroperoxybenzene to phenol and acetone, and the purification of phenol are known in the literature, for example, as in U.S. Patent 5, 160,497 and U.S. Patent No. 5,01 7,729, the oxidation step of cumene to cumene hydroperoxide can be carried out, for example, at a temperature in the range of 60 to 150 ° C and in the range of 1 to 1 kg - The pressure of f/cm 2 is carried out with molecular oxygen. Preferably, it is operated in the presence of an initiator and a pH controlling base compound. The step of converting cumene hydroperoxide to phenol and acetone is carried out, for example, in the presence of a strong acid such as sulfuric acid, or, for example, an exchange resin or ruthenium-aluminum oxide. At the end, the reaction mixture is concentrated to recover acetone' and then recycled to the alkylation step (a). It can be clearly seen how to carry out the process of co-producing water by recycling acetone to step (a) to start the production of phenol from hydrogen, oxygen and benzene. According to a preferred embodiment, at the end of the first step, after the desired product cumene is separated by fractional distillation (transferred to a subsequent oxidation step), the remaining portion of polyisopropylbenzene and benzene are used for transalkylation. The separation step of the reaction recovers the other isopropyl-18- 201041650 benzene. The transalkylation reaction is carried out in the presence of zeolite beta or a zeolite-based catalyst, in particular in accordance with the teachings of EP 687500 and EP 847 802, which also describe the reaction conditions. The acid-containing zeolite (preferably zeolite beta), copper and optionally one or more selected from the group consisting of IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, VIII (limited to iron, bismuth and hungry) The catalyst composition of the present invention, and the elements of the lanthanide elements, are novel and further aspects of the invention. 〇 The catalyst composition is preferably a zeolite-containing beta, copper, and an element selected from the group consisting of chromium and aluminum. The metal contained in the composition is preferably in the form of an oxide. In accordance with a particular aspect of the invention, copper and chromium are present in the form of chromium ore. The copper is preferably contained in the catalyst composition of the present invention in a weight ratio of metal of from 0.001 to 10, more preferably from 0.01 to 2, relative to the zeolite. When the catalyst composition contains one or more elements selected from Groups IIIA, IVA, IIIB, IVB, VB, VIB, VIIB, VIII (limited to iron, strontium and starvation), and lanthanides, each element is more Preferably, the relative zeolite ranges from 0.001 to 10, more preferably 金属 〇. 〇 1 to 2 by weight of the metal. When the metal component of the catalyst composition used in this patent includes chrome ore, cerium and manganese may be present as a promoter. These catalyst compositions may additionally contain binders. These catalyst compositions are prepared in accordance with all of the above methods. The following examples are provided to further describe the invention without limiting its scope. Preparation of Catalyst 1 - Catalyst System A catalyst system was prepared comprising 10 g of chrome ore copper having the following composition (expressed as element -19-201041650% by weight) as a main catalyst (manufactured by Siid Chemie, trade name G99b) : copper 35%, chromium 31%, bismuth 2%, manganese 2.5%, hereinafter referred to as "material A1", and 4.5 g of zeolite beta-based touch prepared in accordance with the instructions of Example 1 of EP 6 8 7500 The media is called "material B1". Zeolite beta for the preparation of material B1 is a product of Zeoly st, under the trade name CP-806 BL 25. The catalyst system is prepared such that the first zone of the system comprises only material A1 equal to 3 grams and the second zone comprises a mechanical mixture of materials A1 and B1 equal to 7 grams of material A1 and 4.5 grams of material B1. Therefore, the total amount of the catalyst system thus prepared is equal to 14.5 grams. The preparation of the complex J-type 2-catalyst system consists of the materials G-9 9b (57 g) and zeolite beta (80 g) which have been used in the above examples, and the alumina p-銶 marketed under the trade name Versal 450 by Laroche. The acid salt (143 g) was started to prepare the catalyst system. The material was mechanically mixed in a plough mixer for about 25 minutes, and then the mixing was not interrupted, and 175 cc of a 5 % w/w aqueous acetic acid solution was added to the thus obtained powder 〇 ^ mixture, which was mixed for about another 20 minutes. The intermediate thus obtained is then subjected to compression using a HUTT-type gear compression extruder, and the thus obtained product is then subjected to aging for not less than about 48 hours. After the aging period, the product in granular form is then at 550. (: The temperature was subjected to sintering treatment for about 5 hours to obtain a material called "material B2" containing about 25% of material G99b, about 30% zeolite beta, and about 45% oxidation bonding carrier. - 201041650 Preparation of a catalyst system comprising a single zone of material B2. The total amount of catalyst system thus prepared is equal to 9.0 grams. Example 3 - Preparation of Catalyst System Preparation of a catalyst system comprising two distinct zones, first zone 3 g of material A1' which had been used in Example 1 and the second zone contained 8 g of material B2 prepared according to the procedure described in Example 2. Therefore, the total amount of the catalyst system was equal to gram. Example 4 - Catalyst System Preparation 37 g of a boiling Q stone beta-catalyst (12-16 mesh) prepared according to the instructions provided in Example 1 of EP 6 87500 was charged into a spinner flask having a volume of 500 ml and then vacuum dried at room temperature 2 A solution comprising 30.34 grams of demineralized water and 8.0 grams of copper nitrate Cu(N03)2.2.5H20 (MW = 23 2.59, 34.4 millimoles) was prepared. The solid was impregnated under vacuum at room temperature. Rotate slowly for 3 hours and then dry in an oven at 120 °C for 2 hours. Sintering at 3 16 ° C / 4 hours at an increasing rate of i ° C min - 1. 18.8 g of product was subjected to secondary impregnation, as before but using 4.06 g of copper niobate Cu(N03) 2, 2.5 H20 (MW = 232.59, 1 7.5 millimoles) and 15.42 grams of demineralized water solution, sintered at 31 6 ° C. The solid is impregnated under vacuum at room temperature and allowed to slowly rotate under vacuum for 3 hours. It was dried in an oven at 0 °C for 2 hours, and burned at 482 ° C / 8 hours at an increasing rate of 1 ° C min · 1. 19.4 g of sintered product (10.29% copper) was recovered. Example 5 - Catalyst test using the following The experimental device was subjected to a catalyst test. -21 - 201041650 The experimental device includes a reagent tank of benzene and acetone, a feed pump of reagents and acetone, a mass meter for controlling the flow rate of hydrogen from the gas cylinder, and before the reagent enters the reaction. Static mixer, reagent preheating unit, steel reactor inside the electric oven (temperature regulation in the oven and reactor), pressure regulation system inside the reactor (by air valve), cooler for reaction solution, And liquid and gaseous product collection systems. The reactor inside the oven comprises a steel cylinder line with a mechanical seal system and an internal diameter equal to about 2 cm. The enthalpy along the main shaft of the reactor has a temperature trap equal to 1 mm in diameter, which can be along the reactor main axis and thus along the catalytic bed. A thermocouple in which the spindle was free to move. A catalyst system (size ranging from 1 to 2 mm) prepared as described in Example 1 was charged into the reactor in an amount equal to 14.5 grams such that the total height of the catalyst bed was equal to 8.5 cm. The quantitative inert quartz material is placed under the catalyst bed with a catalyst bed equal to 2 cm and a lower 2 cm height. The catalyst was then dried in a nitrogen stream at a temperature equal to 160 ° C inside the reactor for 1 hour, followed by a low pressure hydrogen stream of 5.2 ml/min for 60 minutes, followed by 15.8 ml/min of hydrogen at 180 ° C. The feed was fed for 120 minutes, and finally a 23.6 ml/min hydrogen stream was fed at 200 ° C for 180 minutes, then the hydrogen feed was stopped and the reactor temperature was returned to equal to 150 ° C. The experimental apparatus was continuously maintained at In the nitrogen stream. - But at a fixed temperature of 150 ° C, the nitrogen flow is stopped and the benzene feed is started at a flow rate equal to 0.245 milliliters per minute. The system was maintained under these conditions for 60 minutes and then started at a flow rate equal to -22-201041650 27.3 ml/min of hydrogen feed, and after a few minutes the start-up flow rate was equal to 0.012 ml/min of acetone feed. About 3 hours after the acetone feed, the liquid and gaseous portions of the reaction solution were removed and analyzed by gas chromatography. Table 1 summarizes the operating conditions and the results obtained. In this table: - WHSV represents the ratio of the sum of the hourly flow rate of benzene to acetone (without hydrogen) and the amount of catalyst system; an [aryl] / [acetone] selectivity indicates conversion to cumene + polyiso The ratio of acetone to the total amount of acetone converted from propylbenzene (product of decylation to produce cumene); - [cumene] / [acetone] selectivity indicates the relative conversion of acetone to cumene. The ratio of the total amount; - [aryl] / [benzene] selectivity indicates the ratio of acetone converted to total benzene converted to cumene + polyisopropylbenzene. Example 6 - Catalyst Test The catalyst test was carried out using the same experimental apparatus as in Example 5 and the same experimental conditions, but loaded with a catalyst system prepared according to Example 2 in an amount equal to 9 grams, the total height of the catalyst bed Equal to 8.3 cm. The benzene was fed at a flow rate equal to 0.184 ml/min. About 3 hours after the start of the acetone feed, the liquid and gaseous portions of the reaction solution were removed and analyzed by gas chromatography. Table 1 summarizes the operating conditions and the results obtained. Example 7 - Catalyst Test The catalyst system was tested using the same experimental apparatus as in Example 5 and the same experimental conditions, but loaded with a catalyst system prepared according to Example 3 in an amount equal to 11 grams. The total height of the bed is equal to 8.5 cm. The benzene was fed at a flow rate equal to 251.251 ml/min. About 3 hours after the start of the acetone feed, the liquid and gaseous portions of the reaction solution were removed and analyzed by gas chromatography. Table 1 summarizes the operating conditions and the results obtained. Example 8 - Catalyst Test The catalyst test was carried out using the same experimental apparatus as in Example 5 and the same experimental conditions, but loaded with a catalyst system prepared according to Example 3 in an amount equal to 11 grams, the total height of the catalyst bed Equal to 8.5 cm. Acetone was fed at a flow rate equal to 0.009 ml/min and benzene was fed at a flow rate equal to 0-072 ml/min. About 3 hours after the start of the acetone feed, the liquid and gaseous portions of the reaction solution were removed and analyzed by gas chromatography. Table 1 summarizes the operating conditions and the results obtained. Example 9 - Catalyst Test 触 Catalyst testing was performed using the same experimental setup as in Example 5 and the same experimental conditions, but with a catalyst system prepared in accordance with Example 4 in an amount equal to 5 grams, the total height of the catalyst bed was equal to 5 cm. The catalyst was then dried in a stream of nitrogen and the temperature inside the reactor was raised from 120 ° C to 190 ° C in about 2 hours. Once a fixed temperature of 190 ° C was reached, the nitrogen flow was aborted and the benzene feed was started at a flow rate equal to 0.254 ml/min. The system was maintained under these conditions for 60 minutes, then a hydrogen feed having a flow rate equal to 27.3 ml/min was started, and after a few minutes the start flow rate was equal to 0.036 ml/min -24- 201041650 acetone feed. About 3 hours after the acetone feed, the liquid and gaseous portions of the reaction solution were removed and analyzed by gas chromatography. Table 1 summarizes the operating conditions and the results obtained. Table 1 Example number 5 6 7 8 9 The amount of catalyst system (eg 14.5 9 11 11 5 reaction temperature (°c) 150 150 150 150 190 reaction pressure (kpa) 100 100 100 100 100 total WHSV (1T1) 0.9 1.1 1.2 0.4 3.0 [benzene y [acetone 1 molar ratio 16.8 12.6 17.2 6.3 5.8] / [acetone] molar 7.4 7.4 7.4 9,77 2.5 acetone conversion rate 100.0 100 100 100 98,5 [aryl y [ Acetone 1 selectivity % 96.6 88.3 94.6 980 89% 1 [cumene] / [acetone] selectivity % 81.9 70.2 79.8 79.7 81.0 [aryl benzene] selectivity % 99.4 96.7 99.0 99.8 96.7 Example 10 - Catalyst system Preparation of a material comprising copper aluminate as the main catalyst (manufactured by Siidchemie 'brand name 9, hereinafter referred to as "material A2j, which has the following composition (expressed as % by weight of the element): _ 39.3%, Aluminum bismuth 5.5%, zinc 6.0%, manganese 6.8%), zeolite beta and oxidized and alumina are the same materials used in the above examples. 173 grams of alumina, 192 grams of zeolite beta, P-citrate The zeolite beta shovel mixer mechanically mixes about 124 grams of T4489 into the plow for a minute and then does not interrupt the mixing. -25- 201041650 400 cc of 2% w/w aqueous acetic acid was added to the powder mixture thus obtained, and mixed for about 60 minutes. Then the intermediate obtained was subjected to extrusion using a HUTT-type gear compression extruder, and the obtained product was obtained. Accepting aging for not less than about 48 hours 〇 After the aging period, the product in granular form is then subjected to sintering treatment for about 5 hours in air at room temperature to obtain a material called "material B3", which contains About 30% copper aluminate T4489, about 40% zeolite beta, and about 30% aluminum oxide lanthanum binder. The catalyst system is prepared such that it comprises two distinct zones, the first zone containing 3 grams of material A2, and the second The zone contains 7 grams of material B3 prepared as described. Thus, the total amount of catalyst system is equal to 10 grams.Example 1 Preparation of 1-Catalyst System Preparations include copper aluminate T4489 and zeolite beta which have been used in the above examples. Material: 298 g of zeolite beta, 255 g of T4489 were placed in a plough mixer and mechanically mixed for about 60 minutes, then 3 65 cc of 5% w/w acetic acid aqueous solution was added without interruption. Powder mixture, mix for another 20 minutes 〇 The HUTT-type gear compression extruder is then used to subject the resulting intermediate to extrusion and the resulting product is then subjected to aging for a period of not less than about 48 hours. 〇 After the aging period, the product in granular form is then at about 550. (: The temperature was subjected to sintering treatment for 5 hours to obtain a material called "Material B4" containing about 50% copper aluminate T4489 and about 50% zeolite beta. Preparation of the catalyst system -26-201041650 Two distinct zones, the first zone containing 3 grams of material A2, and the second zone containing 7 grams of material B4 prepared as described. Thus, the total amount of catalyst system is equal to 10 grams. Example 12 - Catalyst Test Use Catalyst testing was performed on the same experimental setup of Example 5. The catalyst system (size 1 to 2 mm) prepared as described in Example 10 was charged to the reactor in an amount equal to 10 grams so that the total height of the catalyst bed was equal to 8.5 cm. 定量 The quantitative inert quartz material is placed under the catalyst bed with the catalyst bed equal to 2 cm and the lower 2 cm height. Then the catalyst is dried in the nitrogen stream for 1 hour, at which time the internal temperature rises. To 210 ° C. Once this temperature is reached, feed 1.3 ml / min of benzene stream for about 30 minutes. Then reduce the temperature to 194 ° C, increase the pressure to 2100 Kpa, and stop the nitrogen flow. Then 367 ml /min of hydrogen feed for about 30 minutes. Finally stop the benzene feed, and will be 0.77 grams /min of benzene and acetone solution [C6] / [C3] = 6.3 flow feed. ^ About 3 hours after the start of acetone feed, the liquid and gaseous fractions of the solution are taken from the reaction, followed by gas chromatography Analysis. The sampling operation was repeated in the same analysis step about 24 hours after the start of the feed. Table 2 summarizes the operating conditions and the results obtained. Example 13 - Catalyst Testing The same experimental apparatus as described in Example 5 was used and The catalyst test was carried out under the same experimental conditions as in Example 12. The catalyst system prepared according to Example 11 (size range of 1 to 2 mm) was charged into the reaction -27-201041650 in an amount equal to 10 grams. The total height of the catalyst bed is equal to 8.1 cm. About 3 hours after the start of the acetone feed, the liquid and gaseous fractions of the eluate are taken from the reaction and analyzed by gas chromatography. About 24 hours after the start of the feed, The sampling operation was repeated in the same analytical step. Table 2 summarizes the operating conditions and the results obtained. Example 14 - Catalyst Testing The same experimental apparatus as described in Example 5 was used and the catalyst test was performed under the same experimental conditions as in Example 12. ,but A catalyst system prepared as described in Example 3, with a total amount equal to 11 grams, has a total catalyst bed height equal to 8.3 cm. A flow of 0.76 g/min of benzene and acetone solution [C6]/[C3] = 6.3 Feeding. About 3 hours after the start of the acetone feed, the liquid and gaseous fractions of the eluate were taken from the reaction and analyzed by gas chromatography. About 24, 73 and 3 84 hours after the start of the feed, The sampling operation was repeated in the same analysis step. Table 2 summarizes the operating conditions and the results obtained. Example 15 - Catalyst test The catalyst test was carried out using the same experimental apparatus as described in Example 5, but the amount was equal to 11 g. The catalyst system prepared as described in Example 3 had a total catalyst bed height equal to 8.4 cm. The catalyst was dried in a nitrogen stream at a temperature equal to 160 ° C for 1 hour, then a hydrogen stream of 5.2 ml/min was fed at a low pressure for 60 minutes, followed by a hydrogen flow of 15-8 ml/min at 180 ° C. The feed was fed for 120 minutes and finally a 23.6 ml/min hydrogen stream was fed at 200 ° C for 180 minutes. The hydrogen feed is then stopped and the reactor temperature is returned to a temperature equal to 170 ° C. The experimental unit is maintained in the nitrogen stream 〇-28- 201041650 - but at a fixed temperature of 170 ° C, the nitrogen flow is stopped and equal to 0.36 ml. The flow rate of /min starts the benzene feed. Increase the pressure to 850 Kpa. The system was maintained under these conditions for 60 minutes and then the hydrogen feed was started at a flow rate equal to 338 ml/min; the benzene feed was stopped after a few minutes, and the benzene and acetone solution [C6]/[C3] was 0.76 g/min. = 6.3 Flow feed. About 3 hours after the start of the acetone feed, a sample of the liquid and gaseous fractions was taken from the reaction and analyzed by gas chromatography. Table 2 summarizes the operating conditions and the results obtained. Example 16 - Catalyst Test The catalyst test was carried out using the same experimental apparatus as described in Example 5, but with a catalyst system prepared in an amount equal to 11 grams as described in Example 3, the total height of the catalyst bed was equal to 8.4 cm. . The catalyst was allowed to dry in a stream of nitrogen for 1 hour at which time the temperature inside the reactor was raised to 23 (TC. Once this temperature was reached, a 1.3 ml/min benzene stream was fed for about 30 minutes. Then the temperature was lowered. At 210 ° C, the pressure was raised to 2900 Kpa, the nitrogen flow was stopped, and a hydrogen stream of 3 67 ml/min was fed for about 30 minutes. Finally, the benzene feed was stopped, and the benzene and acetone solution was 0.76 g/min. [C6]/[C3] = 6.3 Flow Feeding Approximately 20 hours after the start of the acetone feed, a sample of the liquid and gaseous fractions was taken from the reaction and analyzed by gas chromatography. Table 2 Summary of Operating Conditions And the results obtained. (5) Schematic description of the first example of the catalyst system preparation (la~If) where 1 refers to the metal component of the catalyst composition; -29- 201041650 A solid acid with alkylating functional group Ingredients; AI refers to a composition containing hydrogenated and alkylated functional groups. FIG. 2 is a flow chart of a process for producing a product of the present invention.
-30- 201041650-30- 201041650
u> t— 8 V o 2900 5 CO «> 11.9 100.0 Θ6.9 83.8 99J2 *〇 T" s: V § 5 CO <d 10.8 100.0 962 τ— 99.3 CO S x- § 5 CO cd 10.8 1100.0 ：68.7 99.6 啼 s rt s 2100 ;· CO (d 11.9 100.0 97.0 76.2 的.1 T~ T" *r- 2100 5 CO <d 119 100.0 97.7 i_ CO s 的_3 S ▼— s V· 2100 j 5 <0 <d σ» r· 100.0 97.8 77.0 99.3 to T- S T- 2100 | 5 <0 11.9 100.0 97.7 76.9 992 CO v~ CN 〇 在 χ— 2100 丨 t£> <0 <〇 11.9 100.0 f^.8 i 73.7 98.8 CO 〇 s "t- 210) <〇 CO <D 11.9 100.0 97.β 73.9 98.7 ca «5 o s X— 2100 _I CD CO (d 11.9 100.0 97.8 76.7 99.0 i CO o z •c— 2100 CC> CO 11,9 100.0 97.8 76,6 98.8 mm 流時間 （h> 觸媒系統之登 （s) i 反應溫度 （°c) 反應麼力 Μ) 總 whsvot1) 【苯w丙鲖】莫耳比拥 [ΗΜ丙銅】莫耳比网 丙®轉化率 ㈨ [芳基y[丙as I 1擇性（％) g 1' 糊 K 与： E 咪 [芳基M苯.]遘擇性（％) -31 -u> t— 8 V o 2900 5 CO «> 11.9 100.0 Θ6.9 83.8 99J2 *〇T" s: V § 5 CO <d 10.8 100.0 962 τ— 99.3 CO S x- § 5 CO cd 10.8 1100.0 : 68.7 99.6 啼s rt s 2100 ;· CO (d 11.9 100.0 97.0 76.2 of .1 T~ T" *r- 2100 5 CO <d 119 100.0 97.7 i_ CO s _3 S ▼ — s V· 2100 j 5 <0 <d σ» r· 100.0 97.8 77.0 99.3 to T- S T- 2100 | 5 <0 11.9 100.0 97.7 76.9 992 CO v~ CN 〇在χ—2100 丨t£><0< 〇11.9 100.0 f^.8 i 73.7 98.8 CO 〇s "t- 210) <〇CO <D 11.9 100.0 97.β 73.9 98.7 ca «5 os X—2100 _I CD CO (d 11.9 100.0 97.8 76.7 99.0 i CO oz •c— 2100 CC>CO 11,9 100.0 97.8 76,6 98.8 mm Flow time (h> Catalyst system (s) i Reaction temperature (°c) Reaction force Μ) Total whsvot1) [Benzene w丙鲖】莫耳比[ΗΜ丙铜】莫尔比网® conversion rate (9) [aryl y [c is as I 1 selectivity (%) g 1' paste K with: E imi [aryl M benzene .] Selectiveness (%) -31 -