201235334 六、發明說明： 〔優先權要求〕 本申請案主張2011年2月18日提出之美國臨時申請 案61 /444,33 8及2011年4月7日提出之歐洲申請案 11161515.9之優先權，其揭示整體倂入本文作爲參考。 【發明所屬之技術領域】 本發明係關於一種製備環己基苯之方法。 【先前技術】 環己基苯是一種在化學工業上逐漸重要之產物，因爲 彼提供製備酚之赫克（Hock )方法的替代途徑。赫克方法 是一種三步驟方法，其中利用丙烯將苯烷基化以製備異丙 苯’將該異丙苯氧化成對應之氫過氧化物，然後將該氫過 氧化物裂解以製造等莫耳量之酚及丙酮。 環己基苯之氧化作用有潛力作爲酚之製造的替代途徑 ’因爲彼同時產生環己酮，該環己酮逐漸具有市場且被使 用以作爲工業溶劑及作爲在氧化反應中及在己二酸和環己 酮樹脂類製造中之活化劑。然而，此種替代途徑需要發展 商業上可行之製造環己基苯先質的方法。 多年來已知：直接藉由利用環己烯之烷基化作用或藉 由氫烷基化作用或環原性烷基化作用之方法可以從苯製造 環己基苯。在後項方法中，苯與氫在觸媒存在下加熱，以 使該苯進行部分氫化作用以製備環己烯，然後環己烯將苯 -5- 201235334 原料烷基化。因此，美國專利4,094,91 8及4，177，165揭 示：在包含經鎳及稀土處理之沸石及鈀促進劑之觸媒上， 芳族烴的氫烷基化作用。同樣地，美國專利4,1 22,1 25及 4,206,082揭示：在經稀土處理之沸石上所承載之釕及鎳化 合物作爲芳族氫烷基化觸媒的用途。在這些先前技藝方法 中所利用之沸石是沸石 X及 Y »此外，美國專利 5,05 3,5 7 1建議使用在冷沸石上所承載之釕及鎳作爲芳族 氫烷基化觸媒。然而，對於苯的氫烷基化作用之這些之前 的建議有以下問題：特別在經濟上可行之苯轉化率下環己 基苯的選擇率是低的且產生大量之不想要的副產物》 最近，美國專利6,03 7,5 1 3已揭示：在苯之氫烷基化 作用中，環己基苯之選擇率可藉由使苯及氫與包含至少一 種氫化金屬及MCM-22族之分子篩的雙官能觸媒接觸而改 良。該氫化觸媒較佳選自鈀、釕、鎳、鈷及其混合物且該 接觸係在約50 °C至350 °C之溫度、約1〇〇至7000 kP a壓 力、約0.01至100之苯對氫之莫耳比及約0.01至100之 WHSV (每小時之重量空間速度）下進行。該‘513專利揭 示：然後可將所得之環己基苯氧化成對應之氫過氧化物且. 該氫過氧化物分解成所要之酚及環己酮。 然而，雖然MCM-22族觸媒之使用已明顯地增加產物 選擇率，藉由直接烷基化作用及藉由苯之氫烷基化作用二 者製造環己基苯仍易於附帶同時產生明顯量之副產物。更 普遍的汙染物之一是多環己基苯類，其典型地最多是轉化 產物之20重量％。因此，爲要使整體方法經濟可行，需要 -6- 201235334 將這些多環己基苯類轉化成另外有用之單環己基苯產物。 將多環己基苯類轉化成另外之單環己基苯的可能方法 是藉由利用另外之苯（其在該‘513專利中稱爲溶劑）的烷 基化作用’其係藉由在含有如該氫烷基化觸媒中所用之相 同的分子篩的觸媒（亦即MCM-2 2族觸媒）存在下但在該 氫烷基化觸媒上沒有該金屬成分且沒有共進料氫的情況下 進行轉烷化作用。其他之轉烷化方法係描述於美國專利 6,489,529 及我們的共同申請中之 PCT 申請案 PCT/EP2008/006072 及 PCT/US20 1 0/03 1 029 中。 從副產物多環己基苯類製備另外之環己基苯的另一方 法係描述於我們的申請中的PCT申請案PCT/201 1 /02353 7 (Attorney Docket2010EM093 )中且包含在酸觸媒（諸如 至少一種鋁矽酸鹽、鋁磷酸鹽或矽鋁磷酸鹽）的存在下之 多環己基苯類的脫烷基化作用。 以上之將多環己基苯類轉化成另外之有用的單環己基 苯產物的方法需要在起初將該多環己基苯類與其餘之該烷 基化或氫烷基化方法的流出物分離。這通常是藉由多階段 分餾方法進行，其中未反應之苯及環己基苯產物在連續的 分餾階段中由該方法流出物移除，留下含有該多環己基苯 類之c12 +餾份。隨意地，該c12 +餾份另外被分餾以將重 物流從該多環己基苯類沖洗出。現在，爲要達成令人滿意 之分離作用，每一分餾階段必須在真空及相對高溫度下操 作。此種操作不僅是昂貴的，並且在商業設定中，真空操 作可能導致空氣進入及，因此，經氧化之烴類的形成。這 -7- 201235334 不僅導致有價値之產物的損失，該氧化之烴類可將在下游 之轉烷化作用或多聚環己基苯類之脫烷基化作用中所用之 觸媒鈍化。 依照本發明，現已發現：藉由一或多種（：,至Cu烴類 或氫或C4至C6烴類（諸如在氣相中），射入分離裝置（ 例如分餾單元），可以促進環己基苯從苯與環己烯之反應 流出物中的多環己基苯類分離出。此步驟使該分餾單元可 在大氣壓或接近大氣壓及中等的底部溫度（典型是約190 °C至約300°C，特別是約190°C至約241°C )下操作。 【發明內容】 在一方面，本發明在於一種製備環己基苯之方法，該 方法包含： (a) 使苯與環己烯在足以製造環己基苯及至少一種多環 己基苯的條件下反應； (b) 將包含至少一部份之該環己基苯及至少一部份之該 至少一種多環己基苯的進料供應至分離裝置以將該 進料分離成至少富含該環己基苯之第一餾份及富含 該至少一種多環己基苯的第二餾份；以及 (e)將包含至少一種Ci-Cu烴或氫之汽提劑在低於（b) 中之進料供應至該分離裝置的位置上分開地供應至 分離裝置。 方便地，該汽提劑是C4-C6烴諸如苯。 方便地，該汽提劑是一種蒸氣。 -8 - 201235334 方便地’該汽提劑在約190 °C至約241 °C之溫度下被 供應至（c)中的該分離裝置。 方便地，供應至（c)中之該分離裝置之該汽提劑的 重量對供應至（b)中之該分離裝置的反應產物的重量的 比是約〇 _ 〇 5 : 1至約2 : 1，諸如約〇 · 1 : 1至約1 : 1，例如約 0.5:1。 方便地，該分離裝置包含分餾塔且該汽提劑在該分餾 塔底部上或附近被供應。 在一具體例中，該汽提劑包含苯。方便地，至少部份 之供應至（c)中的分離裝置的該苯蒸氣係由在（a)中所 產生之反應產物中所含的未反應的苯獲得。 在一具體例中，在（a)中所利用之環己烯係藉由在 該反應區中苯之原位氫化作用製備。方便地，苯之氫化作 用及反應（a)係在包含MCM-22族之含金屬沸石的觸媒 存在下進行。 在另一方面，本發明在於一種製備環己基苯之方法， 該方法包含： (a)在第一反應區中在足以製備未反應之苯、環己 基苯及至少一種多環己基苯的條件下利用氫將苯氫烷基化 » (b )分開地將（i ) 一種包含至少一部份之該未反應 的苯、該環己基苯及至少一部份之該至少一種多環己基苯 的進料；及（Π) —種包含至少一種C^-Cu烴或氫之汽提劑 供應至分離裝置以分離成至少一種富含環己基苯之第一餾 -9 - 201235334 份及一種富含該至少一種多環己基苯的第二餾份 汽提劑在比進料供應至該分離裝置之點低的位置 至該分離裝置；及 (C)在苯存在下，將至少一部份之來自第 該至少一種多環己基苯轉烷化以製備包含另外之 的產物。 【實施方式】 在本文中所述的是一種製備環己基苯的方法 由使苯與環己烯反應以製備環己基苯及至少一種 苯。然後將該環己基苯及至少一種多環己基苯與 —種Ci-Cu烴或氫（諸如（：4-(：6烴）的汽提劑較 中一同饋至分離裝置，以促進進料分離成至少富 苯之第一餾份及富含至少一種多環己基苯之第二 以下將更詳細描述的，該環己基苯係由該第一餾 然後通常轉化成酚及環己酮，然而在該第二餾份 少一種多環己基苯係利用苯脫烷基化或轉烷基化 外之環己基苯。 環己基苯之製造 在本方法之起初步驟中，環己基苯係藉由在 化官能之觸媒存在下及在促進以下反應之條件下 己烯接觸而製備： ，其中該 上被提供 二餾份之 環己基苯 ，其係藉 多環己基 包含至少 佳在氣相 含環己基 餾份。如 份回收， 中之該至 以產生另 具有烷基 使苯與環 10- 201235334201235334 VI. INSTRUCTIONS: [Priority Claims] This application claims the priority of US Provisional Application No. 61/444,33 8 filed on February 18, 2011, and European Application No. 11161515.9 filed on April 7, 2011, It is hereby incorporated by reference in its entirety. TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing cyclohexylbenzene. [Prior Art] Cyclohexylbenzene is a product that is increasingly important in the chemical industry because it provides an alternative route to the Hock process for the preparation of phenol. The Heck process is a three-step process in which propylene is alkylated with propylene to produce cumene, which is oxidized to the corresponding hydroperoxide, which is then cleaved to produce a molar. Amount of phenol and acetone. Oxidation of cyclohexylbenzene has the potential to be an alternative to the manufacture of phenols' because it produces cyclohexanone at the same time, the cyclohexanone is gradually marketed and used as an industrial solvent and as in the oxidation reaction and in adipic acid and An activator in the manufacture of cyclohexanone resins. However, this alternative approach requires the development of commercially viable methods for the manufacture of cyclohexylbenzene precursors. It has been known for many years that cyclohexylbenzene can be produced from benzene directly by alkylation with cyclohexene or by hydroalkylation or cycloalkylation. In the latter method, benzene and hydrogen are heated in the presence of a catalyst to partially hydrogenate the benzene to produce cyclohexene, and then cyclohexene alkylates the benzene-5-201235334 starting material. Thus, U.S. Patent Nos. 4,094,91,8,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Similarly, U.S. Patent Nos. 4,1,22,1,25 and 4,206,082 disclose the use of ruthenium and nickel compounds supported on rare earth treated zeolites as aromatic hydrogenation alkylation catalysts. The zeolites utilized in these prior art processes are zeolites X and Y. In addition, U.S. Patent 5,05 3,5,7 1 suggests the use of rhodium and nickel supported on cold zeolites as aromatic hydroalkylation catalysts. However, these previous proposals for the hydroalkylation of benzene have the following problems: particularly in the economically viable benzene conversion, the selectivity of cyclohexylbenzene is low and a large amount of unwanted by-products are produced. U.S. Patent No. 6,03,5,1 3 discloses that in the alkylation of benzene, the selectivity of cyclohexylbenzene can be achieved by reacting benzene and hydrogen with a molecular sieve comprising at least one hydrogenation metal and MCM-22 group. Improved by bifunctional catalyst contact. The hydrogenation catalyst is preferably selected from the group consisting of palladium, ruthenium, nickel, cobalt and mixtures thereof and the contact is at a temperature of from about 50 ° C to 350 ° C, a pressure of from about 1 Torr to 7000 kPa, and a benzene of from about 0.01 to 100. The molar ratio of hydrogen to the WHSV of about 0.01 to 100 (weight space velocity per hour) is carried out. The '513 patent discloses that the resulting cyclohexylbenzene can then be oxidized to the corresponding hydroperoxide and the hydroperoxide is decomposed into the desired phenol and cyclohexanone. However, although the use of the MCM-22 family of catalysts has significantly increased the product selectivity, the manufacture of cyclohexylbenzene by direct alkylation and by the hydrogenation of benzene is still prone to incidental simultaneous yields. by-product. One of the more common contaminants is polycyclohexylbenzene, which is typically at most 20% by weight of the conversion product. Therefore, in order to make the overall process economically viable, it is necessary to convert these polycyclohexylbenzenes to another useful monocyclohexylbenzene product, -6-201235334. A possible method of converting polycyclohexylbenzenes to additional monocyclohexylbenzenes is by utilizing the alkylation of additional benzene, which is referred to as the solvent in the '513 patent, by In the presence of a catalyst of the same molecular sieve used in the hydroalkylation catalyst (ie, MCM-2 Group 2 catalyst) but without the metal component on the hydroalkylation catalyst and without co-feed hydrogen Perform transalkylation. Other methods of transalkylation are described in U.S. Patent No. 6,489,529, issued to PCT application Serial No. PCT/EP2008/006072 and PCT/US20 1 0/03 1 029. Another method for the preparation of additional cyclohexylbenzene from the by-product polycyclohexylbenzene is described in PCT Application No. PCT/201 1/02353 7 (Attorney Docket 2010 EM093) in our application and contained in an acid catalyst (such as at least Dealkylation of polycyclohexylbenzenes in the presence of an aluminosilicate, aluminophosphate or yttrium aluminum phosphate. The above process for converting polycyclohexylbenzene to another useful monocyclohexylbenzene product requires separation of the polycyclohexylbenzene from the remainder of the alkylation or hydroalkylation process. This is typically carried out by a multi-stage fractionation process in which unreacted benzene and cyclohexylbenzene products are removed from the process effluent in a continuous fractionation stage, leaving a c12+ fraction containing the polycyclohexylbenzene. Optionally, the c12+ fraction is additionally fractionated to flush the heavy stream from the polycyclohexylbenzene. Now, in order to achieve a satisfactory separation, each fractionation stage must be operated under vacuum and at relatively high temperatures. Such operations are not only expensive, but in commercial settings, vacuum operation can result in air ingress and, therefore, formation of oxidized hydrocarbons. This -7-201235334 not only results in the loss of valuable hydrazine products, but the oxidized hydrocarbons can passivate the catalyst used in downstream transalkylation or dealkylation of polycyclohexylbenzenes. According to the present invention, it has been found that by one or more (:, to Cu hydrocarbons or hydrogen or C4 to C6 hydrocarbons (such as in the gas phase), injection into a separation device (e.g., fractionation unit) can promote cyclohexyl The benzene is separated from the polycyclohexylbenzenes in the reaction effluent of benzene and cyclohexene. This step allows the fractionation unit to be at or near atmospheric pressure and a moderate bottom temperature (typically from about 190 ° C to about 300 ° C). In particular, the invention resides in a process for the preparation of cyclohexylbenzene, which comprises: (a) benzene and cyclohexene are sufficient The reaction is carried out under conditions of producing cyclohexylbenzene and at least one polycyclohexylbenzene; (b) supplying a feed comprising at least a portion of the cyclohexylbenzene and at least a portion of the at least one polycyclohexylbenzene to a separation device Separating the feed into a first fraction enriched in at least the cyclohexylbenzene and a second fraction enriched in the at least one polycyclohexylbenzene; and (e) comprising at least one Ci-Cu hydrocarbon or hydrogen The stripping agent is supplied to the separation device at a feed lower than (b) The stripping agent is conveniently supplied to the separation device. Conveniently, the stripping agent is a C4-C6 hydrocarbon such as benzene. Conveniently, the stripping agent is a vapor. -8 - 201235334 Conveniently the stripping agent is at about 190 ° The separation device is supplied to the separation device in (c) at a temperature of C to about 241 ° C. Conveniently, the weight of the stripping agent supplied to the separation device in (c) is supplied to (b) The weight ratio of the reaction product of the separation device is from about 〇 〇 5 : 1 to about 2 : 1, such as from about 〇 1 : 1 to about 1: 1, for example about 0.5: 1. Conveniently, the separation device comprises fractionation And the stripping agent is supplied on or near the bottom of the fractionation column. In one embodiment, the stripping agent comprises benzene. Conveniently, at least a portion of the benzene vapor supplied to the separation unit of (c) It is obtained from unreacted benzene contained in the reaction product produced in (a). In one specific example, the cyclohexene utilized in (a) is by the original benzene in the reaction zone. Prepared by hydrogenation. Conveniently, the hydrogenation of benzene and the reaction (a) are carried out in a catalyst containing a metal-containing zeolite of the MCM-22 family. In another aspect, the invention resides in a process for the preparation of cyclohexylbenzene, the process comprising: (a) sufficient to produce unreacted benzene, cyclohexylbenzene, and at least one polycyclohexylbenzene in the first reaction zone Alkylation of benzene with hydrogen under conditions » (b) separately comprising (i) at least a portion of the unreacted benzene, the cyclohexylbenzene, and at least a portion of the at least one polycyclohexyl group a feed of benzene; and (Π) a stripping agent comprising at least one C^-Cu hydrocarbon or hydrogen supplied to a separation device to be separated into at least one cyclohexylbenzene-rich first fraction-9 - 201235334 and one a second fraction stripping agent enriched in the at least one polycyclohexylbenzene to a lower portion than a point at which the feed is supplied to the separation device; and (C) at least a portion in the presence of benzene The at least one polycyclohexylbenzene is transalkylated to produce an additional product. [Embodiment] Described herein is a method for producing cyclohexylbenzene by reacting benzene with cyclohexene to prepare cyclohexylbenzene and at least one benzene. The cyclohexylbenzene and at least one polycyclohexylbenzene are then fed to the separation unit together with a stripping agent of Ci-Cu hydrocarbon or hydrogen (such as (: 4-(:6 hydrocarbon)) to promote feed separation. Forming at least a first fraction of benzene-rich fraction and a second, enriched in at least one polycyclohexylbenzene, wherein the cyclohexylbenzene is converted from the first fraction to the phenol and cyclohexanone, however, The second fraction is less than one polycyclohexylbenzene system. The cyclohexylbenzene is dealkylated or transalkylated with benzene. Manufacture of cyclohexylbenzene In the initial step of the method, cyclohexylbenzene is used in the process. Prepared by contacting a hexene in the presence of a functional catalyst under conditions which promote the following reaction: wherein the second fraction is provided with a cyclohexylbenzene having a polycyclohexyl group containing at least a cyclohexyl group in the gas phase. If it is recycled, it should be used to produce another alkyl group to make benzene and ring 10-201235334
0 + 0 可將該環己烯以與該苯分開的進料形式供應至該反應 區，但一般是藉由在氫化成分（其係在具有烷基化官能之 觸媒上所提供的）的存在下將苯選擇性氫化而在原位上製 備。該雙官能觸媒因此在本文中是指氫烷基化觸媒且整體 而言該氫烷基化反應進行如下以製備環己基苯（CHB ):0 + 0 The cyclohexene can be supplied to the reaction zone in a feed form separate from the benzene, but is generally provided by a hydrogenation component which is provided on a catalyst having an alkylation function. The benzene is selectively hydrogenated in the presence of an in situ preparation. The bifunctional catalyst thus refers herein to a hydroalkylation catalyst and, in general, the hydroalkylation reaction proceeds as follows to produce cyclohexylbenzene (CHB):
在該氫烷基化作用中可以使用任何商業上可得之苯進 料，但較佳地該苯具有至少99重量％之純度。同樣地，雖 然氫源不特別嚴定，但通常想要使該氫具有至少99重量％ 純度。 方便地，送至該氫烷基化作用之全部進料含有少於 1 000 ppm，諸如少於500 ppm，例如少於1 〇〇 ppm之水。 此外，全部的進料一般含有少於100 ppm，諸如少於30 ppm ’例如少於3 ppm之硫及少於1 〇 ppm，諸如少於1 ppm，例如少於0· 1 ppm之氮。 可將廣範圍値的氫供應至該氫院基化作用，但一般被 安排以使在該氣院基化作用中氫對苯之莫耳比在約〇.15:1 至約1 5 : 1之間，諸如在約0 · 4 : 1至約4 : 1之間，例如在約 -11 - 201235334 0.4至約0.9:1之間。 除了該苯及氫之外，可將在氫烷基化作用條件下基本 上爲惰性之稀釋劑供應至該氫烷基化反應。典型地’該稀 釋劑是可溶解所要之環烷基芳族產物（在此情況中係環己 基苯）的烴，諸如直鏈烷烴、支鏈烷烴、及/或環烷烴。 適合之稀釋劑實例是癸烷及環己烷。環己烷是特別具有吸 引力之稀釋劑，因爲彼是該氫烷基化反應之不想要的副產 物。 雖然稀釋劑之量並未狹窄地定義，通常該稀釋劑之添 加量是使該稀釋劑對該芳族化合物的重量比爲至少1:100 :例如至少1 :1 0，但不多於1 0 :1，典型地不多於4:1。 該氫烷基化反應可以在多種反應器構型中進行，包括 固定床、漿液反應器及/或催化蒸餾塔。此外，該氫烷基 化作用可在單一反應區中或在多個反應區中進行，其中將 至少該氫在各階段中導至該反應。適合之反應溫度是在約 l〇〇°C至約400°c之間，諸如在約125t至250°c之間，同 時適合之壓力是在約1 00至約7,000 kPa之間，諸如在約 500至約5,000 kPa之間。 在該氫烷基化反應中所用之觸媒是包含MCM-22族分 子篩及氫化金屬之雙官能觸媒。如在本文中所用之“MCM-22族材料”（或“MCM-22族之材料”或“MCM-22族分子篩” )包含以下之一或多種： •由普通之第一度結晶建構嵌段單位晶格構成之分子 篩，該單位晶格具有 MWW網絡外形（framework -12- 201235334 topology )。（單位晶格是多個原子之空間排列，其若鋪 設於三維空間中則描述該晶體結構。此種晶體結構在 “Atlas of Zeolite Framework Types”2001 年第 5 版中討論 ，其整個內容被合倂作爲參考）； •由普通之第二度建構嵌段構成之分子篩，其爲二維 鋪設之此種MWW網絡外形單位晶格，形成具有一個單位 晶格厚度的單層，較佳是一個c單位晶格厚度； •由普通之第二度建構嵌段構成之分子篩，其爲具有 一或多於一單位晶格厚度的層，其中具有多於一個單位晶 格厚度的層係由堆疊、綑紮或結合至少二個具有一個單位 晶格厚度的單層而製作。此種第二度建構嵌段的堆疊可以 是規則方式、不規則方式、無規方式或其任何組合方式； 及 •藉由任何具有MWW網絡外形之單位晶格的規則或 無規2維或3維組合方式構成的分子篩》 MCM-22族分子篩通常具有包含在12.4±0.25、6.9± 0.15、3.57±0.07 及 3.4 2±0.07 埃之 d 間隔最大値（d-spacing maxima )的X光繞射圖形。將材料（b )特徵化 所用之X光繞射數據係藉由使用Κ- α二重態（K-alpha doublet )之銅作爲入射輻射及配備閃爍計數器及相關電腦 之繞射計作爲收集系統的標準技術獲得。MCM-22族分子 餘包括MCM-22(在美國專利4,954,325中描述）、PSH-3 (在美國專利4,439,409中描述）、SSZ-25(在美國專利 4，826,667中描述）、ERB-1 (在歐洲專利0293032中描述 -13- 201235334 )、ITQ-1 (在美國專利6,077,498中描述）、ITQ-2(在 國際專利公開 W097/1 7290中描述）、MCM-36 (在美國 專利 5,25 0,2 77 中描述）、MCM-49 (在美國專利 5,236,575中描述）、MCM-56(在美國專利 5,362,697中 描述）、UZM-8 (在美國專利6,756,030中描述）、及其 混合物。較佳地，該分子篩係選自（a ) MCM-49、( b ) MCM-56及（c) MCM-49及 MCM-56之同型體，諸如 ITQ-2。 在該氫烷基化觸媒中可以利用任何已知的氫化金屬， 雖然適合的金屬包括鈀、釕、鎳、鋅、錫、及鈷，鈀是特 佳的。通常，在該觸媒中所含之氫化金屬的量是在該觸媒 之約0.05至約10重量％之間，諸如在該觸媒之約0.1至 約5重量％之間。在該MCM-22族分子篩是鋁矽酸鹽的具 體例中，所含之氫化金屬的量是使在該分子篩中之鋁對該 氫化金屬的莫耳比爲約1.5至約1 500，例如約75至約 7 5 0，諸如約1 0 0至約3 0 0。 該氫化金屬可藉由例如浸漬作用或離子交換直接被承 載於該MCM-22族分子篩上。然而，在更佳之具體例中， 至少50重量％，例如至少75重量％及通常基本上全部的 該氫化金屬被承載於一種與該分子篩分開卻複合之無機氧 化物上。特別地，據發現：藉由將該氫化金屬承載於該無 機氧化物上，該觸媒之活性及其對環己基苯及二環己基苯 的選擇性，與相同但該氫化金屬被承載於該分子篩上的觸 媒比較，是增加的。 -14- 201235334 在此種複合的氫化觸媒中所用的無機氧化物並未狹窄 地被定義’只要彼在該氫烷基化反應條件下是安定且惰性 的。適合之無機氧化物包括元素週期表第2、4、13及14 族之氧化物，諸如氧化鋁、氧化鈦及/或氧化锆。如本文 中所用的’週期表族群之編號體制係如Chemical and Engineering News，63 ( 5)，27 ( 1985)中所揭示的。 在一具體例中’在該含金屬之無機氧化物與該分子篩 複合之前’方便地藉由浸漬將該氫化金屬沉積在該無機氧 化物上。典型地，該觸媒複合材料係藉由以下方式製造： 共九化作用（co-pelletization)，其中該分子篩與該含金 屬之無機氧化物的混合物在高壓力（通常是約350至約 350,000 kPa)下形成九粒；或共擠出作用，其中將該分子 篩及該含金屬之無機氧化物的漿液並隨意地與一分開的黏 合劑驅流過模具。若需要，隨後可將另外之氫化金屬沉積 在所得之觸媒複合材料上。 適合之黏合劑材料包含合成或天然生成之物質以及無 機材料’諸如黏土、矽石及/或金屬氧化物。無機材料可 以是天然生成的或凝膠狀沉澱物或凝膠形式的，其包含矽 石及金屬氧化物之混合物。可作爲黏合劑之天然生成的黏 土包括那些屬於蒙脫土及高嶺土族群者，該族群包含變膨 潤石及一般已知爲 Dixie、McNamee、Georgia 及 Florida 黏土之高嶺土類及其他之主礦物成分爲多水高嶺石、高嶺 石、狄克石、珍珠石或富矽高嶺石者。此類黏土可以原初 之礦物的或起初進行煅燒、酸處理或化學改質之原料狀態 -15- 201235334 被使用。適合之金屬氧化物黏合劑包含矽石、氧化鋁、氧 化錐、氧化鈦、矽石-氧化鋁、矽石-氧化鎂、矽石一氧 化錐、砂石一氧化钍、砂石-氧化鈹、砂石-氧化鈦以及 三元組成物諸如矽石-氧化鋁一氧化钍、矽石-氧化鋁-氧化锆、砂石_氧化鋁_氧化鎂及砂石-氧化鎂-氧化锆 環己基苯產物之處理 雖然使用MCM-22族沸石觸媒的氫烷基化反應對環己 基苯是高度選擇性的，來自該氫烷基化反應之液態流出物 ，除了含有所要之環己基苯之外，將不可避免地含有顯著 量之未反應的苯及某些副產物。主要副產物之一是多環己 基苯（二及/或三環己基苯），其一般是該轉化產物之最 多20重量％。在不同具體例中，來自該氫烷基化反應之流 出物含有，以該流出物之總重量計，至少1重量％，或至 少5重S %，或至少1 0重量％之多環己基苯。一般想要將 這些多環己基苯轉化成另外有用之環己基苯產物。這可藉 由轉烷化作用或脫烷化作用達成，但起初想要將該多環己 基苯與所要產物分離。 在本方法中，該多環己基苯類之分離係藉由將至少一 部份之包含環己基苯、一或多種多環己基苯及隨意地未反 應之苯的進料（例如來自該氣院基化反應）供應至分離裝 置（例如分餾裝置，正常是分餾塔），以將該進料分成至 少一富含環己基苯之第一餾份及富含該一或多種多環己基 -16- 201235334 苯的第二飽份。當餾份在所指定之物質中描述成“富含”時 ’彼是指：在該餾份中，該所指定之物質的重量％相對於 該進料流（亦即輸入）是豐富的。 在一具體例中，爲使該分離能在大氣壓或接近大氣壓 (約100 kP a至約300 kPa)及相對低溫度下進行，包含 至少一種C^-Cn烴或氫之汽提劑被分開地供應至該分離裝 置。在多種具體例中，該汽提劑是C4至C6烴，諸如苯。 在多種具體例中，該汽提劑在氣相中被供應。方便地，該 汽提劑係在約190°C至約300°C之溫度下被供應至（c)中 之分離裝置。更特別地，在使用蒸氣以加熱且蒸發該汽提 劑的情況中，供應至（c)中之該分離裝置的該汽提劑蒸 氣的溫度是在約1 9 0 °C至約2 4厂C之間。 在另一具體例中，該汽提劑係在液相中被供應至該分 離裝置且在原位上加熱成蒸氣相或部分蒸氣相。通常，供 應至該分離裝置之該汽提劑蒸氣的重量對供應至該分離裝 置之進料的重量的比是約0.05:1至約2:1，諸如約0.1:1 至約1 :1，例如約0.5 :1。 在一具體例中，在比將包含環己基苯、一或多種多環 己基苯、及隨意地未反應之苯的進料供應至該分離裝置的 點低的位置上，供應該汽提劑。在一具體例中，汽提劑烴 被供應至該分離裝置之下半。在一具體例中，該汽提劑係 在該分餾塔之底部或其附近被供應。雖然可以使用任何汽 提劑烴蒸氣，苯蒸氣是特別有用的，因爲該氫烷基化反應 流出物含有明顯量（典型是高達60重量％)之未反應的苯 -17- 201235334 在本方法之一具體例中，在與該氫烷基化反應流出物 分離之後’該多環己基苯類與苯混合且轉烷化以製造另外 之單環己基苯。轉烷化作用典型是在一個與該氫烷基化反 應器分離之轉烷化反應器中，於合適之轉烷化觸媒（諸如 MCM-22族之分子篩、沒沸石、MCM-68 (參見美國專利 6,014,018) 、Y沸石及絲光沸石）上進行。該轉烷化反 應典型是在至少部分液相條件下之進行，該條件合適地包 括約100°C至約30(TC之溫度、約800 kPa至約3500 kPa 之壓力、整個進料約1 hr·1至約1 〇 hr·1之每小時之重量空 間速度及約1:1至約5:1之苯/二環己基苯重量比。 在本方法之另一具體例中，多環己基苯轉化成另外之 單環己基苯係藉由脫烷化作用進行。脫烷基化作用或裂解 典型地在一個與該氫烷基化反應器分離之反應器（諸如反 應蒸餾單元）中，在約150°C至約500°C之溫度及15 psig 至5 00 psig(2 00 kPa至3550 kPa)之壓力下，在酸觸媒 (諸如鋁矽酸鹽、鋁磷酸鹽、矽鋁磷酸鹽、非結晶之矽 石-氧化鋁、酸黏土、混合之金屬氧化物（諸如W0x/Zr02 )、磷酸、硫酸化之氧化銷及其混合物）上進行。通常， 該酸觸媒包含至少一種鋁矽酸鹽、鋁磷酸鹽或矽鋁磷酸鹽 。脫烷基化作用可以在不添加苯之情況下進行，雖然可能 想要將苯添加至該脫烷基化反應以減少焦炭形成。在此情 況中，脫烷基化反應之進料中苯對多烷基化之芳族化合物 的重量比典型是〇至約0.9，諸如約0.01至約0.5。同樣 -18- 201235334 地’雖然該脫烷基化反應可以在不添加氫之情況下進行， 氫通常被導入該脫烷基化反應器中以幫助減少焦炭。適合 之氫添加速率是使在該脫烷基化反應器之整個進料中氫對 多烷基化之芳族化合物的莫耳比是約0.01至約10。在共 同申請中之申請案PCT/20 1 0/03 1 029中更詳細描述多種脫 烷基化方法。 該氫烷基化反應之另一明顯的副產物是環己烷。雖然 包含環己烷及未反應之苯的富（：6物流可以藉由蒸餾作用 容易地從該氫烷基化反應流出物移除，但因苯及環己烷沸 點之相似性，該富C6物流難以藉由簡單之蒸餾作用進一 步被分離。然而，一些或所有的該富（:6物流可再循環至 該氫烷基化反應器以不僅提供部分的苯進料，也提供部分 的上述稀釋劑。 在某些情況中，可能想要將一些富C6物流供應至脫 氫化反應區，其中該富c6物流在足以將在該富c6物流部 份中之至少部份之該環己烷轉化成苯的脫氫化條件下與脫 氫化觸媒接觸，該苯可再度再循環至該氫烷基化反應。該 脫氫化觸媒通常包含（a)載體；（b)氫化-脫氫化成分 ;及（c)無機促進劑。方便地，該載體（a)係選自矽石 、矽酸鹽、鋁矽酸鹽、氧化錐及碳奈米管（nanotubes)， 且較佳包含矽石。適合之氫化-脫氫化成分（b)包含至 少一種選自元素週期表第6至10族的金屬，諸如鈾、鈀 及其化合物和混合物。典型地，該氫化-脫氫化成份含量 是在觸媒的約0.1至約10重量％之間。適合之無機促進劑 -19- 201235334 (C)包含至少一種選自元素週期表第1族之金屬或化合 物，諸如鉀化合物。典型地，該促進劑含量是在該觸媒的 約0.1至約5重量％之間。適合之脫氫化條件包含約250 t：至約500°C之溫度、約大氣壓至約500 psig(i〇〇 kPa至 3 550 kPa)之壓力、約0.2 hr·1至50 hr·1之每小時之重量 空間速度及約〇至約20之氫對烴進料的莫耳比。 氫烷基化反應之其他不利的雜質是二環己烷（BCH ) 及甲基環戊基苯（MCPB )異構物，由於其沸點類似性， 其係難以藉由蒸餾從所要之環己基苯分離出。再者，雖然 1，2_甲基環戊基苯（2-MCPB )及1,3-甲基環戊基苯（3-MCPB )在隨後之氧化/裂解步驟中易於轉化成有價値之 產物-酚及甲基環戊酮類，1，1-甲基環戊基苯（1-MCPB ) 對氧化作用基本上是惰性的，且因此若不移除，則將包含 在該C12物流中》同樣地，二環己烷（BCH)會造成下游 之分離問題。Any commercially available benzene feed may be used in the hydroalkylation, but preferably the benzene has a purity of at least 99% by weight. Likewise, although the hydrogen source is not particularly critical, it is generally desirable to have the hydrogen at least 99% by weight pure. Conveniently, all of the feed to the hydroalkylation contains less than 1 000 ppm, such as less than 500 ppm, such as less than 1 〇〇 ppm of water. In addition, all feeds typically contain less than 100 ppm, such as less than 30 ppm', such as less than 3 ppm sulfur, and less than 1 〇 ppm, such as less than 1 ppm, such as less than 0.1 ppm nitrogen. A wide range of helium hydrogen can be supplied to the hydrogen radicalization, but is generally arranged such that the hydrogen to benzene molar ratio in the gasification of the gas is between about 1515.1 to about 15:1. Between, for example, between about 0 · 4 : 1 to about 4 : 1, for example between about -11 - 201235334 0.4 to about 0.9: 1. In addition to the benzene and hydrogen, a diluent which is substantially inert under hydroalkylation conditions can be supplied to the hydroalkylation reaction. Typically the diluent is a hydrocarbon which will dissolve the desired cycloalkyl aromatic product, in this case cyclohexylbenzene, such as linear alkanes, branched alkanes, and/or cycloalkanes. Examples of suitable diluents are decane and cyclohexane. Cyclohexane is a particularly attractive diluent because it is an undesirable by-product of the hydroalkylation reaction. Although the amount of diluent is not narrowly defined, the diluent is usually added in an amount such that the diluent has a weight ratio to the aromatic compound of at least 1:100: for example at least 1:10, but not more than 1 0 :1, typically no more than 4:1. The hydroalkylation reaction can be carried out in a variety of reactor configurations, including fixed bed, slurry reactors, and/or catalytic distillation columns. Furthermore, the hydroalkylation can be carried out in a single reaction zone or in a plurality of reaction zones, wherein at least the hydrogen is directed to the reaction in each stage. Suitable reaction temperatures are between about 1 ° C to about 400 ° C, such as between about 125 t and 250 ° c, while a suitable pressure is between about 100 and about 7,000 kPa, such as at about 500 to about 5,000 kPa. The catalyst used in the hydroalkylation reaction is a bifunctional catalyst comprising a molecular sieve of MCM-22 and a hydrogenation metal. As used herein, "MCM-22 family materials" (or "MCM-22 family materials" or "MCM-22 family molecular sieves") comprise one or more of the following: • Building blocks by ordinary first degree crystallization A molecular sieve composed of a unit lattice having a MWW network shape (framework -12-201235334 topology). (The unit cell is a spatial arrangement of a plurality of atoms, which is described in the three-dimensional space. This crystal structure is discussed in the 5th edition of the "Atlas of Zeolite Framework Types" 2001, and the entire content is combined.倂 as a reference); • a molecular sieve consisting of a common second-degree building block, which is a two-dimensionally laid MWW network unit cell, forming a single layer having a unit lattice thickness, preferably a c Unit lattice thickness; a molecular sieve composed of a common second degree building block, which is a layer having one or more unit lattice thicknesses, wherein the layer system having more than one unit lattice thickness is stacked and bundled Or made by combining at least two single layers having a unit lattice thickness. The stack of such second constructed blocks may be in a regular manner, an irregular manner, a random manner, or any combination thereof; and • a rule or random 2D or 3 by any unit lattice having a MWW network profile Molecular Sieves of Dimensional Combinations MCM-22 Group Molecular Sieves typically have X-ray diffraction patterns containing d-spacing maxima at 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07, and 3.4 2 ± 0.07 angstroms. . The X-ray diffraction data used to characterize material (b) is used as a standard for collection systems by using copper of Κ-α doublet (K-alpha doublet) as incident radiation and a diffractometer equipped with a scintillation counter and associated computer. Technology is obtained. The MCM-22 family of molecules includes MCM-22 (described in U.S. Patent 4,954,325), PSH-3 (described in U.S. Patent 4,439,409), SSZ-25 (described in U.S. Patent 4,826,667), and ERB-1 (in European Patent No. 0293032 describes -13-201235334), ITQ-1 (described in US Patent 6,077,498), ITQ-2 (described in International Patent Publication No. W097/1 7290), MCM-36 (in US Patent 5,250) , MJ-49 (described in U.S. Patent No. 5,236,575), MCM-56 (described in U.S. Patent No. 5,362,697), UZM-8 (described in U.S. Patent No. 6,756,030), and mixtures thereof. Preferably, the molecular sieve is selected from the group consisting of (a) MCM-49, (b) MCM-56 and (c) MCM-49 and MCM-56 isoforms, such as ITQ-2. Any known hydrogenation metal may be utilized in the hydroalkylation catalyst, although suitable metals include palladium, rhodium, nickel, zinc, tin, and cobalt, with palladium being preferred. Typically, the amount of hydrogenation metal contained in the catalyst is between about 0.05 and about 10 weight percent of the catalyst, such as between about 0.1 and about 5 weight percent of the catalyst. In the specific example wherein the MCM-22 family molecular sieve is an aluminosilicate, the amount of the hydrogenation metal is such that the molar ratio of aluminum to the hydrogenation metal in the molecular sieve is from about 1.5 to about 1,500, for example, about 75 to about 7 5 0, such as from about 1 0 0 to about 300. The hydrogenation metal can be directly supported on the MCM-22 family molecular sieve by, for example, impregnation or ion exchange. However, in a more preferred embodiment, at least 50% by weight, such as at least 75% by weight and usually substantially all of the hydrogenation metal is supported on an inorganic oxide which is separated from the molecular sieve but which is complexed. In particular, it has been found that by carrying the hydrogenation metal on the inorganic oxide, the activity of the catalyst and its selectivity to cyclohexylbenzene and dicyclohexylbenzene are the same but the hydrogenation metal is carried on the catalyst. The comparison of the catalyst on the molecular sieve is increased. -14- 201235334 The inorganic oxides used in such complex hydrogenation catalysts are not narrowly defined as long as they are stable and inert under the hydroalkylation reaction conditions. Suitable inorganic oxides include oxides of Groups 2, 4, 13 and 14 of the Periodic Table of Elements, such as alumina, titania and/or zirconia. The numbering system of the 'periodic table population' as used herein is as disclosed in Chemical and Engineering News, 63 (5), 27 (1985). In a specific example, the hydrogenation metal is conveniently deposited on the inorganic oxide by impregnation before the metal-containing inorganic oxide is combined with the molecular sieve. Typically, the catalyst composite is made by co-pelletization wherein the mixture of the molecular sieve and the metal-containing inorganic oxide is at a high pressure (typically from about 350 to about 350,000 kPa). Forming nine particles; or coextruding, wherein the molecular sieve and the slurry of the metal-containing inorganic oxide are optionally driven through a mold with a separate binder. If desired, additional hydrogenation metal can then be deposited on the resulting catalyst composite. Suitable binder materials include synthetic or naturally occurring materials as well as inorganic materials such as clay, vermiculite and/or metal oxides. The inorganic material may be in the form of a naturally occurring or gelatinous precipitate or gel comprising a mixture of vermiculite and a metal oxide. Naturally occurring clays that can be used as binders include those belonging to the montmorillonite and kaolin populations, which contain variable bentonites and kaolin clays commonly known as Dixie, McNamee, Georgia and Florida clays and other major mineral components. Water kaolinite, kaolinite, Dickstone, pearl stone or rich kaolinite. Such clays can be used as raw materials or raw materials that are initially calcined, acid treated or chemically modified -15-201235334. Suitable metal oxide binders include vermiculite, alumina, oxidized cone, titanium oxide, vermiculite-alumina, vermiculite-magnesia, vermiculite oxide cone, sandstone niobium oxide, sandstone-yttria, Sand-titania and ternary compositions such as vermiculite-alumina cerium oxide, vermiculite-alumina-zirconia, sandstone_alumina_magnesia and sandstone-magnesia-zirconia cyclohexylbenzene product Treatment Although the hydroalkylation reaction using a MCM-22 family of zeolite catalysts is highly selective for cyclohexylbenzene, the liquid effluent from the hydroalkylation reaction, in addition to the desired cyclohexylbenzene, will Inevitably, a significant amount of unreacted benzene and certain by-products are contained. One of the main by-products is polycyclohexylbenzene (di- and/or tricyclohexylbenzene), which is generally up to 20% by weight of the conversion product. In various embodiments, the effluent from the hydroalkylation reaction contains at least 1% by weight, or at least 5 % by weight, or at least 10% by weight, based on the total weight of the effluent, of polycyclohexylbenzene. . It is generally desirable to convert these polycyclohexylbenzenes to additional useful cyclohexylbenzene products. This can be achieved by transalkylation or dealkylation, but initially it was desirable to separate the polycyclohexylbenzene from the desired product. In the method, the polycyclohexylbenzene is separated by at least a portion of a feed comprising cyclohexylbenzene, one or more polycyclohexylbenzenes, and optionally unreacted benzene (eg, from the gas plant) The basement reaction) is supplied to a separation unit (eg, a fractionation unit, which is normally a fractionation column) to separate the feed into at least one first fraction rich in cyclohexylbenzene and enriched in the one or more polycyclohexyl-16- 201235334 The second fullness of benzene. When a fraction is described as "enriched" in a given substance, it is meant that in the fraction, the weight percent of the specified material is abundant relative to the feed stream (i.e., input). In one embodiment, the stripping agent comprising at least one C^-Cn hydrocarbon or hydrogen is separately prepared for the separation to be carried out at or near atmospheric pressure (about 100 kPa to about 300 kPa) and at relatively low temperatures. Supply to the separation device. In various embodiments, the stripping agent is a C4 to C6 hydrocarbon such as benzene. In various embodiments, the stripping agent is supplied in the gas phase. Conveniently, the stripping agent is supplied to the separation device in (c) at a temperature of from about 190 ° C to about 300 ° C. More particularly, in the case where steam is used to heat and evaporate the stripping agent, the temperature of the stripping agent vapor supplied to the separating apparatus in (c) is from about 190 ° C to about 2 4 Between C. In another embodiment, the stripping agent is supplied to the separation unit in the liquid phase and heated in situ to form a vapor phase or a portion of the vapor phase. Typically, the ratio of the weight of the stripping agent vapor supplied to the separation unit to the weight of the feed to the separation unit is from about 0.05:1 to about 2:1, such as from about 0.1:1 to about 1:1. For example, about 0.5:1. In one embodiment, the stripping agent is supplied at a lower position than the point at which the feed containing cyclohexylbenzene, one or more polycyclohexylbenzenes, and optionally unreacted benzene is supplied to the separation device. In one embodiment, stripping agent hydrocarbons are supplied to the lower half of the separation unit. In one embodiment, the stripping agent is supplied at or near the bottom of the fractionation column. Although any stripping agent hydrocarbon vapor can be used, benzene vapor is particularly useful because the hydroalkylation reaction effluent contains significant amounts (typically up to 60% by weight) of unreacted benzene-17-201235334 in the process. In one embodiment, the polycyclohexylbenzene is mixed with benzene and transalkylated after separation from the hydroalkylation reaction effluent to produce additional monocyclohexylbenzene. The transalkylation is typically carried out in a transalkylation reactor separated from the hydroalkylation reactor in a suitable transalkylation catalyst (such as molecular sieves of the MCM-22 family, zeolite-free, MCM-68 (see U.S. Patent 6,014,018), Y zeolite and mordenite are carried out. The transalkylation reaction is typically carried out under at least a portion of the liquid phase conditions, suitably comprising from about 100 ° C to about 30 (temperature of TC, a pressure of from about 800 kPa to about 3500 kPa, and the entire feed is about 1 hr) • an hourly weight space velocity of from 1 to about 1 〇hr·1 and a weight ratio of benzene to dicyclohexylbenzene of from about 1:1 to about 5:1. In another embodiment of the method, polycyclohexylbenzene Conversion to additional monocyclohexylbenzene is carried out by dealkylation. Dealkylation or cleavage is typically carried out in a reactor (such as a reactive distillation unit) separated from the hydroalkylation reactor. From 150 ° C to about 500 ° C and pressure from 15 psig to 500 psig (200 kPa to 3550 kPa) in acid catalysts (such as aluminosilicate, aluminophosphate, yttrium aluminum phosphate, non- Crystallized vermiculite-alumina, acid clay, mixed metal oxides (such as W0x/Zr02), phosphoric acid, sulfated oxidation pins, and mixtures thereof. Typically, the acid catalyst comprises at least one aluminosilicate. , aluminophosphate or yttrium aluminum phosphate. Dealkylation can be carried out without adding benzene, although It may be desirable to add benzene to the dealkylation reaction to reduce coke formation. In this case, the weight ratio of benzene to polyalkylated aromatic compound in the feed to the dealkylation reaction is typically from about 〇 to about 0.9, such as from about 0.01 to about 0.5. The same -18-201235334, 'Although the dealkylation reaction can be carried out without the addition of hydrogen, hydrogen is typically introduced into the dealkylation reactor to help reduce coke. A suitable rate of hydrogen addition is such that the molar ratio of hydrogen to polyalkylated aromatic compounds throughout the feed to the dealkylation reactor is from about 0.01 to about 10. Application in the co-pending application PCT/ A variety of dealkylation processes are described in more detail in 20 1 0/03 1 029. Another significant by-product of the hydroalkylation reaction is cyclohexane, although rich in cyclohexane and unreacted benzene (: The stream 6 can be easily removed from the hydroalkylation reaction effluent by distillation, but due to the similarity of the boiling points of benzene and cyclohexane, the C6-rich stream is difficult to be further separated by simple distillation. Some or all of this rich (:6 logistics can be recycled to The hydroalkylation reactor provides not only a portion of the benzene feed but also a portion of the above diluent. In some cases, it may be desirable to supply some C6-rich stream to the dehydrogenation reaction zone, wherein the rich C6 stream The benzene can be recycled to the hydroalkylation reaction in contact with a dehydrogenation catalyst under dehydrogenation conditions sufficient to convert at least a portion of the cyclohexane in the rich C6 stream portion to benzene. The dehydrogenation catalyst generally comprises (a) a support; (b) a hydrogenation-dehydrogenation component; and (c) an inorganic promoter. Conveniently, the support (a) is selected from the group consisting of vermiculite, citrate, and aluminosilicate. And oxidized cones and carbon nanotubes, and preferably containing vermiculite. Suitable hydrogenation-dehydrogenation component (b) comprises at least one metal selected from Groups 6 to 10 of the Periodic Table of Elements, such as uranium, palladium, and compounds and mixtures thereof. Typically, the hydrogenation-dehydrogenation component is present in an amount between about 0.1 and about 10% by weight of the catalyst. Suitable inorganic promoters -19- 201235334 (C) comprise at least one metal or compound selected from Group 1 of the Periodic Table of the Elements, such as a potassium compound. Typically, the promoter level is between about 0.1 and about 5% by weight of the catalyst. Suitable dehydrogenation conditions include a temperature of from about 250 t: to about 500 ° C, a pressure of from about atmospheric pressure to about 500 psig (i kPa to 3 550 kPa), and an hourly hour of about 0.2 hr·1 to 50 hr·1. The weight space velocity and the molar ratio of hydrogen to hydrocarbon feed to about 20 Torr. Other unfavorable impurities in the hydroalkylation reaction are dicyclohexane (BCH) and methylcyclopentylbenzene (MCPB) isomers, which are difficult to distill from the desired cyclohexylbenzene due to their similar boiling point. Separated. Furthermore, although 1,2-methylcyclopentylbenzene (2-MCPB) and 1,3-methylcyclopentylbenzene (3-MCPB) are easily converted into products of valuable ruthenium in the subsequent oxidation/cracking step. - phenol and methylcyclopentanone, 1,1-methylcyclopentylbenzene (1-MCPB) is essentially inert to oxidation and, if not removed, will be included in the C12 stream" Similarly, dicyclohexane (BCH) causes downstream separation problems.
U-甲基環戊基苯U-methylcyclopentylbenzene
因此，至少部份之該氫烷基化反應產物可在各種條件 下利用觸媒處理以將至少1,1-甲基環戊基苯及/或二環己 烷從該產物移除。該觸媒通常是酸觸媒諸如鋁矽酸鹽沸石 ’且特別地是八面沸石，且該處理係在約1 〇 〇 °c至約3 5 0 °C (諸如約130°C至約250°C )之溫度下進行約〇_1至約3 -20- 201235334 小時，諸如約ο. 1至約1小時。據相信：該催化處理將該 1,1-甲基環戊基苯異構化成更易氧化之1，2-甲基環戊基苯 (2-MCPB )及1 ,3-甲基環戊基苯（3-MCPB )。據相信： 二環己烷依照以下反應與在該氫烷基化反應產物中所含之 苯反應以製備環己烷及更想要之環己基苯。Thus, at least a portion of the hydroalkylation reaction product can be treated with a catalyst under various conditions to remove at least 1,1-methylcyclopentylbenzene and/or dicyclohexane from the product. The catalyst is typically an acid catalyst such as an aluminosilicate zeolite and in particular a faujasite, and the treatment is from about 1 ° C to about 350 ° C (such as from about 130 ° C to about 250). A temperature of about 〇_1 to about 3 -20 to 201235334 hours, such as about ο. 1 to about 1 hour. It is believed that the catalytic treatment of the isomerization of 1,1-methylcyclopentylbenzene to 1,2-methylcyclopentylbenzene (2-MCPB) and 1,3-methylcyclopentylbenzene which are more oxidizable (3-MCPB). It is believed that dicyclohexane is reacted with benzene contained in the hydroalkylation reaction product in accordance with the following reaction to produce cyclohexane and more desirable cyclohexylbenzene.
C^O+O-OKD+O 〇 該催化處理可以對該氫烷基化反應之直接產物上進行 或在氫烷基化反應產物蒸餾後進行以將該c6及/或重餾 份分離。 將由該氫烷基化反應產物所分離之富含環己基苯之物 流送至在以下更詳細描述之氧化反應。 環己基苯氧化作用 爲要將該環己基苯轉化成酚及環己酮，該環己基苯在 起初被氧化成對應之氫過氧化物。這是藉由將該環己基苯 與含氧氣體（諸如空氣及空氣之多種衍生物）接觸而完成 〇 可以在觸媒存在或不存在下進行氧化。適合之氧化觸 媒包括在美國專利6,720,462中所述之經N-羥基取代之環 醯亞胺類，其爲此目的倂入本文作爲參考。例如，可以使 用N-羥基鄰苯二甲醯亞胺（NHPI) 、4-胺基-N-羥基鄰苯 二甲醯亞胺、3-胺基-N-羥基鄰苯二甲醯亞胺、四溴-N_羥 基鄰苯二甲醯亞胺、四氯-N -羥基鄰苯二甲醯亞胺、N -羥 -21 - 201235334 基黑特醯亞胺（N-hydroxyhetimide) 、N-羥基欣醯亞胺（ N-hydroxyhimimide) 、N-羥基苯偏三甲醯亞胺、N-羥基 苯-1，2,4-三羧醯亞胺、Ν,Ν’-二羥基（苯均四甲二醯亞胺 )、1>^’-二羥基（二苯甲酮-3,3’，4,4’-四羧二醯亞胺）、 Ν_羥基順丁烯二醯亞胺、吡啶-2，3-二羧醯亞胺、Ν-羥基丁 二醯亞胺、Ν-羥基（酒石醯亞胺）、Ν-羥基-5-降莰烯- 2.3- 二羧醯亞胺、外-Ν-羥基-7-氧雜雙環〔2.2.1〕庚-5-烯- 2.3- 二羧醯亞胺、Ν-羥基-順式-環己烷-1，2-二羧醯亞胺、 Ν-羥基-順式-4-環己烯-1，2-二羧醯亞胺、Ν-羥基萘醯亞胺 鈉鹽或Ν-羥基苯二磺醯亞胺。較佳地，該觸媒是Ν-羥 基鄰苯二甲醯亞胺。另一適合之觸媒是Ν，Ν’，Ν”-三羥基異 三聚氰酸。 這些氧化觸媒可單獨被使用或與自由基起始劑聯合使 用，且另外可用來作爲液相均質觸媒或可被承載在固態載 體上以提供雜相之觸媒。典型地，利用該經Ν-羥基取代 之環醯亞胺或該經Ν，Ν’，Ν”-三羥基異三聚氰酸，其量是在 該環己基苯之0.0001重量％至15重量％之間，諸如在 0.001重量％至5重量％之間》 適合之氧化條件包括在約7 〇 °C及約2 0 0 °C間，諸如約 90°C至約130t之溫度，及約50 kPa至1 0,000 kPa之壓力 。可以添加鹼性緩衝劑以與在該氧化期間可能形成之酸性 副產物反應。此外，可導入水相。該反應可用批次或連續 流動方式進行。 該氧化反應所用之反應器可以是任何能使氧導入環己 -22- 201235334 基苯的反應器，且可另外有效地使氧與環己基苯接觸以進 行該氧化反應。例如，該氧化反應器可包含簡單而大抵開 放之槽，其具有用於含氧物流的散布器入口。在多種具體 例中，該氧化反應器可具有將其部分內容物引流且抽取經 過合適冷卻裝置且使該冷卻的部份返回該反應器的裝置， 藉此管理該氧化反應之放熱。可選擇地，提供間接冷卻（ 亦即藉由冷卻用水）之冷卻用迴圈可以在該氧化反應器內 部操作以移除所產生之熱。在其他具體例中，該氧化反應 器可包含多個串聯的反應器，其分別隨意地在所選之用以 在相關之環己基苯或氧或二者之轉化範圍下加強其內之氧 化反應的不同條件下進行部份的反應。該氧化反應器可以 批次、半批次或連續流動方式進行。 典型地，該環己基苯氧化反應之產物含有，以該氧化 反應流出物總重量計，至少5重量％ ’諸如至少1 0重量％ ，例如至少1 5重量％，或至少2 0重量％之環己基-卜苯基-1-氫過氧化物。通常，該氧化反應流出物含有，以該氧化 反應流出物之總重量計，不多於80重量％ ’或不多於60 重量％，或不多於40重量％，或不多於30重量％，或不多 於25重量％之環己基-1-苯基-1-氫過氧化物。該氧化反應 流出物可另外包含醯亞胺觸媒及未反應之環己基苯。例如 ，該氧化反應流出物可包含未反應之環己基苯，其量以該 氧化反應流出物計，至少50重量％ ’或至少60重量％， 或至少6 5重量％，或至少7 0重量％，或至少8 0重量％， 或至少90重量％。 -23- 201235334 至少一部份之氧化反應流出物可進行裂解反應’而有 或沒有進行任何先前之分離或處理。例如，所有或部分的 氧化反應流出物可進行高真空蒸餾以產生富含未反應之環 己基苯的產物且留下殘留物，該殘留物具有濃縮之所要的 環己基-1-苯基-1-氫過氧化物且進行裂解反應。另外或可 選擇地，所有或部分的氧化流出物、或所有或部分的真空 蒸餾殘留物可被冷卻以引發未反應之醯亞胺氧化觸媒的結 晶作用，而可藉由過濾或藉由刮除將該氧化觸媒從用於進 行該結晶作用之熱交換器表面移除。至少一部份之所得之 減少或不含醯亞胺氧化觸媒的氧化組成物可進行裂解反應 〇 作爲另一實例，所有或部份的該氧化流出物可進行水 洗，然後經過吸附劑（諸如3A分子篩）以將水與其他可 吸附之化合物分離，且提供具有減少之水或醯亞胺含量而 可進行該裂解反應的氧化組成物。同樣地，所有或部分的 該氧化流出物可進行以化學或物理爲基礎之吸附作用，諸 如越過碳酸鈉床上以移除該醯亞胺氧化觸媒（例如NHPI )或其他可吸附之成分，且提供減少氧化觸媒或其他可吸 附成份之含量而可進行裂解反應的氧化組成物。另一可能 的分離作用包含使所有或部分的該氧化流出物與含鹼之液 體（諸如鹼金屬碳酸鹽或碳酸氫鹽之水溶液）接觸以形成 包含該醯亞胺氧化觸媒之鹽的水相及減少醯亞胺觸媒之有 機相。藉由鹼性材料之處理的分離實例揭示於國際申請案 WO 2009/025939 中。 -24- 201235334 氫過氧化物之裂解 在該環己基苯轉化成酚及環己酮時之最終反應步驟包 含在該氧化中所製造之該環己基-1-苯基-1-氫過氧化物之 經酸催化的裂解。 通常，在該裂解反應中所用之該酸觸媒是至少部分溶 於該裂解反應混合物，在至少185 °C溫度下是安定的且具 有比環己基苯低的揮發性（較高的常態沸點）。典型地， 該酸觸媒也是至少部分溶於該裂解反應產物。適合之酸觸 媒是布忍斯特（Brensted)酸及路易士酸，諸如但不限於 磺酸、過氯酸、磷酸、氫氯酸、對苯磺酸、氯化鋁、發煙 硫酸、三氧化硫、氯化鐵、三氟化硼、二氧化硫及三氧化 硫。硫酸是較佳之酸觸媒。 在多種具體例中，該裂解反應混合物含有，以該裂解 反應混合物總重量計，至少50重量份/百萬份（wppm) 且不多於5000 wppm之該酸觸媒’或至少lOOwppm且不 多於3000 wppm之該酸觸媒，或至少150wppm且不多於 2000 wppm之該酸觸媒，或至少300wppm且不多於1500 wPpm之該酸觸媒。 在一具體例中，該裂解反應混合物含有極性溶劑，諸 如含有少於6個碳之醇，諸如甲醇、乙醇、異丙醇及/或 乙二醇；腈，諸如乙腈及/或丙腈；硝基甲烷：及含6或 更少之碳的酮，諸如丙酮、甲基乙基酮、2-或3-戊酮、環 己酮及甲基環戊酮。較佳之極性溶劑是丙酮。通常，將該 -25- 201235334 極性溶劑添加至該裂解反應混合物以使混合物中該極性溶 劑對該環己基苯氫過氧化物之重量比在約1:100至約 100:1之範圍內，諸如約1:20至約10:1，且該混合物包含 約1 0至約40重量％之該環己基苯氫過氧化物。據發現： 該極性溶劑之添加不僅增加在該裂解反應中該環己基苯氫 過氧化物之轉化度，也增加轉化成酚及環己酮之選擇率。 雖然該機轉並未完全了解，但相信：該極性溶劑降低該自 由基引發之環己基苯氫過氧化物轉化成不想要之產物（諸 如己烷苯酮及苯基環己醇）的作用。 在多種具體例中，該裂解反應混合物包含環己基苯， 其量以該裂解反應混合物總重量計，是至少50重量％，或 至少6 0重量％，或至少6 5重量％，或至少7 0重量％，或 至少8 0重量％，或至少9 0重量％。 適合之裂解條件包括至少20°C且不高於200°C，或至 少40°C且不高於120°C之溫度，及至少1 psig且不大於 370 psig (至少7 kPa表壓且不大於2,550 kPa表壓），或 至少14.5 psig且不大於145 psig (至少100 kPa表壓且不 大於l，000 kPa表壓）之壓力，以致該裂解反應混合物在 該裂解反應期間完全或大部份是液相。 用以進行該裂解反應之反應器可以是精於此技藝者已 知的任何形式的反應器。例如，該裂解反應器可以是一種 以接近連續攪拌槽反應器模式操作之簡單且大抵開放的槽 ，或是一種以接近栓狀流反應器模式操作之簡單且未定長 度的管。在其他具體例中，該裂解反應器包含多個串聯之 -26- 201235334 反應器，彼等分別進行一部份之轉化反應，該等反應係隨 意地以不同模式且在所選之在相關轉化範圍下加強裂解反 應的條件下操作。在一具體例中，在該裂解反應器是催化 蒸餾單元。 在多種具體例中，該裂解反應器是可操作以將一部份 之內容物輸送經冷卻裝置且將經冷卻之部分送回該裂解反 應器。可選擇地，該反應器可絕熱地操作。在一具體例中 ，在該裂解反應器中操作之冷卻用迴圈移除任何所產生之 熱。 環己基-1-苯基-1-氫過氧化物之裂解反應的主要產物 是酚及環己酮，二者通常分別可佔該裂解反應產物（諸如 以不包含未反應之環己基苯及酸觸媒計之重量％ )的約40 重量％至約6 0重量％，或約4 5重量％至約5 5重量％。 該裂解產物典型地也含有未反應之酸觸媒且因此至少 一部份之該裂解反應產物可利用鹼性材料中和以移除或減 少產物中之酸濃度。 適合之鹼性材料包含鹼金屬氫氧化物及氧化物、鹼土 金屬氫氧化物或氧化物，諸如氫氧化鈉、氫氧化鉀、氫氧 化鎂、氫氧化鈣、氧化鈣、及氫氧化鋇。隨意地在高溫下 也可使用碳酸鈉及碳酸鉀。 在多種具體例中，該鹼性材料包含以下之一或多種： 苛性交換樹脂（例如磺離子交換樹脂）：氨或氫氧化銨； 鹼性黏土諸如石灰石、白雲石、菱鎂石、海泡石及橄欖石 :活性碳及/或經浸漬之活性碳；陰離子交換樹脂諸如具 -27- 201235334 有苯乙烯一二乙烯基苯聚合物主幹及選自-N(CH3) 2、-NRH或-NR2之胺官能結構的弱鹼性離子交換樹脂，其中R 是氫或含有1至20個碳原子之烷基；利用乙二胺官能化 之胺聚矽氧烷；接枝在微孔性或間隙孔性之金屬氧化物上 的有機鹼性材料：其他有機一無機固體諸如與選自鋰、鈉 、鉀、铷、絶、鈣、鋇、緦及鐳之金屬交換之沸石：利用 選自鋰、鉀、鈉、铷及絶之金屬處理的元素週期表第III 族之氧化物；經承載或固態之鹼、鹼土金屬或有機金屬； 通常由鎂鹽及可溶矽酸鹽之交互作用所衍生之矽酸鎂：具 有鹼性水解作用之鹽諸如乙酸鈉、碳酸氫鈉、苯酚鈉及碳 酸鈉；及胺類諸如一級、二級或三級脂族胺類或芳族胺類 ，例如苯胺、正丁胺、雜環胺類諸如吡啶、哌啶、哌嗪、 三乙胺、脂族或芳族二胺類、及烷醇胺類。特別地，可以 使用其與弱有機酸類之鹽形式的胺類。方便地，該鹼性材 料是二胺諸如2-甲基五伸甲基二胺或六伸甲基二胺，其在 商業上可得自Invista S.& r.l. Corporation，商品名爲 DYTEKtm A 及 DYTEKtm HMD。 適合之固態鹼性材料包括：鹼性金屬氧化物族；在金 屬氧化物上之鹸；在金屬氧化物上之鹼土；鹼及鹼土沸石 :過渡金屬稀土及較高價氧化物；水滑石、燒結之水滑石 及尖晶石，特別是利用選自鋰、鉀、鈉、铷、絶之鹼金屬 及其組合處理之水滑石；鈣鈦礦；及/3 -氧化鋁類。 在一具體例中，該鹼性材料是在美國專利6,201，157 中所描述之位阻胺類的一或多種。將了解：該鹼性材料可 -28- 201235334 以在無水狀態下被添加或可以是任何前述鹼性材料（特別 是該金屬氫氧化物或具有鹼性水解作用之鹽類）的水溶液 〇 方便地’本發明之中和反應中所用之液態鹼性材料（ 諸如已討論之胺或二胺）具有相對低之揮發性與比環己基 苯之常態沸點溫度高之常態沸點溫度，以使該材料易於在 隨後之分餾操作中殘留於底部產物中，該分餾操作係可對 至少一部份之可含此種液態鹼性材料之經處理之裂解反應 產物進行。 . 中和反應之進行條件隨著所利用之酸觸媒及鹼性材料 變化。適合之中和條件包含至少3 01、或至少4 0 °c、或 至少50°C、或至少60°C、或至少70°C、或至少80。(：、或 至少9 0 °C之溫度。其他適合之中和條件包含不高於2 〇 〇。〇 、或不高於190°C、或不高於180°C、或不高於I70t、或 不筒於160°C、或不高於150°C、或不高於14〇t：、或不高 於130 °C、或不高於120。(：、或不高於11〇 t、或不高於 1 〇 〇 °C之溫度。在多種具體例中，該中和條件包含比裂解 反應條件減低之溫度’例如該溫度可以比該裂解反應之溫 度低1 °C、或5 °C、或10 °C、或1 5 °C、或2 01、或3 0乞 、或 40°C。 適合之中和條件可包含約1 psig至約500 psig ( 5 kPa 表壓至3450 kPa表壓），或約l〇 pSig至約200 pSig(7〇 kP a表壓至1380 kP a表壓）之壓力，以使該經處理之裂解 反應混合物在該中和反應期間完全或主要是在液相中。 -29- 201235334 在中和後，該中和之酸產物可從該裂解產物移除，留 下酚及環己酮之粗製混合物，其可藉由在此技藝中習知的 方法純化且分離。 本發明現在將參考所附之圖示更特別地描述，其中圖 1是處理苯之氫烷基化反應產物之一般方法的流程圖，但 圖2是依照本發明之第一實例之處理此種產物之方法的流 程圖。 參考圖1，在該一般方法中，包含環己基苯、一或多 種多環己基苯類及未反應之苯的苯氫烷基化反應之產物經 由管線11送至第一分餾塔12。該反應產物當彼進入該塔 12時典型是在約120°C至約140°C之溫度下且在接近塔底 之點上供應至該塔。在其上端，將該塔12連接至真空源 13，以致該塔12典型地在約20 kP a至約50 kP a之壓力下 操作。在接近該塔12之底部上，可將支流14從該塔移除 ，通過加熱器15且再循環至該塔以致在該塔12底部之溫 度典型是在約20(TC至約24 1 °C之間。 該苯氫烷基化產物係在該塔12中被分餾，以製備富 含未反應之苯的C6餾份及富含環己基苯、多環己基苯類 及其他重物之C12 +餾份。該（：6餾份在該真空源13之輔助 下，從該塔12之上端，經由管線40移除，且可全部或部 分地經由管線1 6再循環至該苯之氫烷基化反應器（未顯 示）。在管線40中之一部分的該物流可部分地再循環至 該塔1 2以作爲迴流之物流1 7，且可部分地經由管線1 8送 至轉烷化反應器1 9。該C , 2 +餾份係經由管線2 1從該塔i 2 -30- 201235334 移除且供應至第二分餾塔22。 該第二塔22之上端係連接至真空源23，以致該塔22 典型地在約10 kPa至約20 kPa之壓力下操作。此外，支 流24可從該塔22之底部附近移除且可以在被再循環至該 塔22之前通過加熱器25，以使在該塔22之底部的溫度典 形式在約220°C至約241°C之間。該C12 +餾份在該塔22中 被分成經由管線41之富含環己基苯的頂部餾份及經由管 線27之富含多環己基苯類之底部餾份。在管線41中之一 部份的頂部餾份經由管線2 6移除以供另外處理該環己基 苯，但該底部餾份經由管線27被供應至第三分餾塔28。 在該管線41中之一部份的物流可再循環至塔22以作爲迴 流物流4 2。 該第三塔28在其上端被連接至高真空源29,以致該 塔28典型地在約1 kP a至約10 kPa之壓力下操作。另外 ，支流31在該塔28之底部附近移除且在被循環至該塔28 之前通過加熱器32，以使在該塔28底部之溫度典型是在 約22(TC至約24 1 °C之間。該塔28將經由管線43而來自 該塔22之頂部餾份分餾成富含多環己基苯類之第一餾份 (其經由管線3 3供應至該轉烷基化反應器1 9 )及經由管 線34移除以供清除或供作爲燃料之重物餾份。在管線43 中之一部份的物流可以再循環至塔2 8以作爲迴流之物流 44 ° 在管線33中之該多環己基苯類與來自管線18之苯在 該轉烷基化反應器19中反應以製造轉烷基化反應流出物 -31 - 201235334 ’該流出物包含主要的環己基苯及未反應之苯，且經由管 線35送回該第一分餾塔12。 現在參考圖2，在依照本發明之方法中，該氫烷基化 反應產物再度送至第一分餾塔111，在此情況中係經由管 線112。再次，支流113可在該塔111之底部附近移除， 通過加熱器114且再循環至該塔。然而此外，由該塔111 之頂部經由管線129所回收之苯在另一加熱器115中預熱 且蒸發且經由管線116注入該塔111之底部。以此方式， 使用加壓之蒸汽加熱該再循環的苯，在該塔111之底部的 溫度可以容易地維持在約1 9 0 °C至約2 4 1 °C之間。在此溫 度下，即使該塔係在大氣壓或大氣壓以上（100 kPa至 3〇〇 kPa)之壓力下操作，基本上所有的該Cl2及較低烴成 份在該塔111之底部上是在蒸汽相中》因此，離開該塔 111之液態底部物流主要是由多環己基苯類及其他重產物 組成且可經由管線1 1 7直接送至轉烷基化反應器1 1 8。 在或稍高於該塔111之中點上，液態支流可從該塔 111移除且藉由管線119送至第二分餾塔121。因爲該支 流基本上不含C18 +烴類，該塔121可在大氣壓力以上（典 型在105 kPa至110 kPa)操作，以將該支流分成富環己 基苯之底部物流及富苯之頂部物流。該富環己基苯之底部 物流可經由管線〗22回收以供另外處理，但該富苯之頂部 物流可經由管線1 2 3返回該塔1 1 1。 爲要在該塔Π1中徵助苯及環己基苯之分離，支流可 例如在該管線1 23的位置上方經由管線1 24從該塔1 1 1移 -32- 201235334 除，且在返回該塔111之前通過冷卻器125。以此 經由管線126離開該塔之氣相頂部物基本上完全由 (C6-)雜質組成。該頂部物起初通過冷凝器127， 輕雜質被移除以供作爲燃料且該苯在通至蒸發單元 前被冷凝。該苯可在該單元128中被加熱且再蒸發 得之苯蒸氣至少部分地經由管線1 29送至該加熱器 部分地經由管線131送至該氫烷基化單元（未顯示 分地經由管線132送至轉烷化反應器1 18。 來自管線132之苯蒸氣及在塔1 1 1底部物之多 苯類（二及三環己基苯二者）在該轉烷化反應器11 應以製造另外之環己基苯。該轉烷化反應器118之 可藉由管線133送至第三分餾塔134，其中未反應 C24+)烴經由底部管線135被移除以供清除且富含 苯之氣相經由頂部管線136移除且送至第一分餾塔 爲使該第三分餾塔134能在大氣壓及低的底部溫度 是約22(TC至約2411 )下操作，來自加熱器1 15 經加熱的苯蒸氣可經由管線137被供應至該塔134 〇 雖然本發明已參考特別具體例描述且說明，一 此技藝之人士將了解本發明本身可有無需在本文中 變化型。因這緣故，僅應參考所附之申請專利範圍 本發明之真實範圍。 【圖式簡單說明】 方式， 苯及輕 其中該 128之 ，且所 115, )且部 環己基 8中反 流出物 之重（ 環己基 111» (典型 之部分 之底部 般精於 說明之 以決定 -33- 201235334 圖1是一般用於處理苯之氫烷基化反應產物的方法流 程圖。 圖2是依照本發明之第一實例之用於處理苯之氫烷基 化反應產物的方法流程圖。 【主要元件符號說明】 11，16，18，21，26, 27, 3 3，34，40，41，43，112，116, 117，119，122，123，124，126，1 29, 1 3 1, 1 3 2, 1 3 3, 1 3 5, 1 3 6，1 3 7 :管線 12，1 1 1 :第一分餾塔 13, 23 ：真空源 14, 24, 31，113 :支流 15, 25, 1 14，1 15 :加熱器 17, 44 :迴流之物流 1 9，1 1 8 :轉烷化反應器 22，121 :第二分餾塔 28，134 :第三分餾塔 29 :高真空源 125 :冷卻器 127 :冷凝器 128 :蒸發單元 -34-C^O+O-OKD+O 〇 The catalytic treatment may be carried out on the direct product of the hydroalkylation reaction or after distillation of the hydroalkylation reaction product to separate the c6 and/or heavy fraction. The cyclohexylbenzene-rich stream separated by the hydroalkylation reaction product is passed to an oxidation reaction as described in more detail below. Oxidation of Cyclohexylbenzene To convert the cyclohexylbenzene to phenol and cyclohexanone, the cyclohexylbenzene is initially oxidized to the corresponding hydroperoxide. This is accomplished by contacting the cyclohexylbenzene with an oxygen-containing gas such as various derivatives of air and air. The oxime can be oxidized in the presence or absence of a catalyst. Suitable oxidizing catalysts include the N-hydroxy substituted cyclononimides described in U.S. Patent No. 6,720,462, the disclosure of which is incorporated herein by reference. For example, N-hydroxyphthalimide (NHPI), 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, Tetrabromo-N-hydroxyphthalic acid imine, tetrachloro-N-hydroxyphthalimide, N-hydroxy-21 - 201235334 N-hydroxyhetimide, N-hydroxyl N-hydroxyhimimide, N-hydroxyphenyltrimethyleneimine, N-hydroxybenzene-1,2,4-tricarboquinone imine, hydrazine, Ν'-dihydroxy (benzotetramethylene)醯imino), 1>^'-dihydroxy (benzophenone-3,3',4,4'-tetracarboxydiimide), hydrazine-hydroxybutyleneimine, pyridine-2 , 3-dicarboxylimine imine, hydrazine-hydroxybutadienimide, hydrazine-hydroxy (tartarium imine), hydrazine-hydroxy-5-norbornene-2.3-dicarboxy quinone imine, external-oxime -hydroxy-7-oxabicyclo[2.2.1]hept-5-ene-2.3-dicarboxy quinone imine, hydrazine-hydroxy-cis-cyclohexane-1,2-dicarboxy quinone imine, hydrazine- Hydroxy-cis-4-cyclohexene-1,2-dicylimine imine, quinone-hydroxynaphthyl imine sodium salt or hydrazine-hydroxy phenyl sulfonimide. Preferably, the catalyst is Ν-hydroxyphthalimide. Another suitable catalyst is ruthenium, Ν', Ν"-trihydroxyisocyanuric acid. These oxidizing catalysts can be used alone or in combination with a free radical initiator, and can also be used as a liquid phase homogeneous touch. The medium may be supported on a solid support to provide a heterogeneous catalyst. Typically, the rhodium-hydroxy substituted cycloheximide or the hydrazine, Ν', Ν"-trihydroxyisocyanuric acid is utilized. The amount is between 0.0001% and 15% by weight of the cyclohexylbenzene, such as between 0.001% and 5% by weight. Suitable oxidizing conditions include at about 7 〇 ° C and about 200 ° C. For example, a temperature of from about 90 ° C to about 130 t, and a pressure of from about 50 kPa to 10 000 kPa. An alkaline buffer may be added to react with acidic by-products that may form during the oxidation. In addition, an aqueous phase can be introduced. The reaction can be carried out in batch or continuous flow mode. The reactor used in the oxidation reaction may be any reactor which can introduce oxygen into the cyclohexene-22-201235334-based benzene, and can additionally effectively contact oxygen with cyclohexylbenzene to carry out the oxidation reaction. For example, the oxidation reactor can comprise a simple, substantially open tank having a diffuser inlet for the oxygen containing stream. In various embodiments, the oxidation reactor can have means for draining a portion of its contents and withdrawing the cooled portion and returning the cooled portion to the reactor, thereby managing the exotherm of the oxidation reaction. Alternatively, a cooling loop that provides indirect cooling (i.e., by cooling water) can be operated inside the oxidation reactor to remove the heat generated. In other embodiments, the oxidation reactor may comprise a plurality of reactors connected in series, optionally arbitrarily selected for enhancing the oxidation reaction therein under the conversion range of the relevant cyclohexylbenzene or oxygen or both. Partial reactions were carried out under different conditions. The oxidation reactor can be carried out in batch, semi-batch or continuous flow. Typically, the product of the cyclohexylbenzene oxidation reaction contains at least 5% by weight, such as at least 10% by weight, such as at least 15% by weight, or at least 20% by weight, based on the total weight of the oxidation reaction effluent Hexyl-Phenyl-1-hydroperoxide. Typically, the oxidation reaction effluent contains no more than 80% by weight or no more than 60% by weight, or no more than 40% by weight, or no more than 30% by weight, based on the total weight of the oxidation reaction effluent Or no more than 25% by weight of cyclohexyl-1-phenyl-1-hydroperoxide. The oxidation reaction effluent may additionally comprise a ruthenium amide catalyst and unreacted cyclohexyl benzene. For example, the oxidation reaction effluent may comprise unreacted cyclohexylbenzene in an amount of at least 50% by weight or at least 60% by weight, or at least 5% by weight, or at least 70% by weight, based on the oxidation reaction effluent , or at least 80% by weight, or at least 90% by weight. -23- 201235334 At least a portion of the oxidation reaction effluent can undergo a cracking reaction with or without any prior separation or treatment. For example, all or part of the oxidation reaction effluent can be subjected to high vacuum distillation to produce a product rich in unreacted cyclohexylbenzene and leaving a residue having the desired cyclohexyl-1-phenyl-1. - Hydroperoxide and undergoing a cleavage reaction. Additionally or alternatively, all or part of the oxidation effluent, or all or part of the vacuum distillation residue, may be cooled to initiate crystallization of the unreacted quinone imide oxidation catalyst by filtration or by scraping In addition to removing the oxidation catalyst from the surface of the heat exchanger used to effect the crystallization. At least a portion of the resulting reduced or free oxidized composition of the ruthenium oxide catalyst can be subjected to a cleavage reaction. As another example, all or part of the oxidative effluent can be washed with water and then passed through an adsorbent (such as 3A molecular sieves) are used to separate water from other adsorbable compounds and provide an oxidizing composition that can be subjected to the cleavage reaction with reduced water or quinone imine content. Likewise, all or part of the oxidation effluent can be subjected to chemical or physical based adsorption, such as over the bed of sodium carbonate to remove the ruthenium oxide catalyst (eg, NHPI) or other adsorbable components, and An oxidizing composition capable of undergoing a cleavage reaction by reducing the content of an oxidation catalyst or other adsorbable component. Another possible separation involves contacting all or part of the oxidation effluent with an alkali-containing liquid, such as an aqueous solution of an alkali metal carbonate or bicarbonate, to form an aqueous phase comprising the salt of the quinone imine oxide. And reducing the organic phase of the ruthenium catalyst. An example of separation by treatment of an alkaline material is disclosed in International Application WO 2009/025939. -24- 201235334 Hydrolysis of Hydroperoxide The final reaction step in the conversion of the cyclohexylbenzene to phenol and cyclohexanone comprises the cyclohexyl-1-phenyl-1-hydroperoxide produced in the oxidation. Acid-catalyzed cleavage. Typically, the acid catalyst used in the cleavage reaction is at least partially soluble in the cleavage reaction mixture, is stable at a temperature of at least 185 ° C and has a lower volatility (higher normal boiling point) than cyclohexylbenzene. . Typically, the acid catalyst is also at least partially soluble in the cleavage reaction product. Suitable acid catalysts are Brensted acid and Lewis acid such as, but not limited to, sulfonic acid, perchloric acid, phosphoric acid, hydrochloric acid, p-benzenesulfonic acid, aluminum chloride, fuming sulfuric acid, trioxide Sulfur, ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide. Sulfuric acid is the preferred acid catalyst. In various embodiments, the cleavage reaction mixture contains at least 50 parts by weight per million (wppm) and not more than 5000 wppm of the acid catalyst or at least 100 wppm and not more than the total weight of the cleavage reaction mixture. The acid catalyst at 3000 wppm, or at least 150 wppm and no more than 2000 wppm of the acid catalyst, or at least 300 wppm and no more than 1500 wPpm of the acid catalyst. In one embodiment, the cleavage reaction mixture contains a polar solvent such as an alcohol containing less than 6 carbons such as methanol, ethanol, isopropanol and/or ethylene glycol; a nitrile such as acetonitrile and/or propionitrile; Methane: and a ketone containing 6 or less carbons such as acetone, methyl ethyl ketone, 2- or 3-pentanone, cyclohexanone and methylcyclopentanone. A preferred polar solvent is acetone. Typically, the-25-201235334 polar solvent is added to the cleavage reaction mixture such that the weight ratio of the polar solvent to the cyclohexylbenzene hydroperoxide in the mixture is in the range of from about 1:100 to about 100:1, such as From about 1:20 to about 10:1, and the mixture contains from about 10 to about 40% by weight of the cyclohexylbenzene hydroperoxide. It has been found that the addition of the polar solvent not only increases the degree of conversion of the cyclohexylbenzene hydroperoxide in the cleavage reaction, but also increases the selectivity to phenol and cyclohexanone. Although the mechanism is not fully understood, it is believed that the polar solvent reduces the conversion of the free radical-initiated cyclohexylbenzene hydroperoxide to undesirable products such as hexane benzophenone and phenylcyclohexanol. In various embodiments, the cleavage reaction mixture comprises cyclohexylbenzene in an amount of at least 50% by weight, or at least 60% by weight, or at least 5% by weight, or at least 70%, based on the total weight of the cleavage reaction mixture. % by weight, or at least 80% by weight, or at least 90% by weight. Suitable cracking conditions include a temperature of at least 20 ° C and no greater than 200 ° C, or at least 40 ° C and no greater than 120 ° C, and at least 1 psig and no greater than 370 psig (at least 7 kPa gauge and no greater than 2,550 kPa gauge), or a pressure of at least 14.5 psig and no greater than 145 psig (at least 100 kPa gauge and no greater than 1 000 kPa gauge) such that the cracking reaction mixture is fully or mostly during the cracking reaction Liquid phase. The reactor used to carry out the cleavage reaction may be any form of reactor known to those skilled in the art. For example, the cleavage reactor can be a simple and generally open tank operating in a near continuous stirred tank reactor mode, or a simple, undetermined length tube operating in a near plug flow reactor mode. In other embodiments, the cleavage reactor comprises a plurality of tandem -26-201235334 reactors, each of which performs a partial conversion reaction, which is optionally in a different mode and selected at the relevant transformation Operate under conditions that enhance the cleavage reaction. In one embodiment, the cleavage reactor is a catalytic distillation unit. In various embodiments, the cleavage reactor is operable to deliver a portion of the contents through a cooling unit and return the cooled portion to the cleavage reactor. Alternatively, the reactor can be operated adiabatically. In one embodiment, the cooling loop operated in the cleavage reactor removes any heat generated. The main products of the cleavage reaction of cyclohexyl-1-phenyl-1-hydroperoxide are phenol and cyclohexanone, which usually account for the cleavage reaction product, respectively (such as to contain unreacted cyclohexylbenzene and acid). From about 40% by weight to about 60% by weight, or from about 45% by weight to about 5% by weight, based on the weight of the catalyst. The cleavage product typically also contains unreacted acid catalyst and thus at least a portion of the cleavage reaction product can be neutralized with a basic material to remove or reduce the acid concentration in the product. Suitable alkaline materials include alkali metal hydroxides and oxides, alkaline earth metal hydroxides or oxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and barium hydroxide. Sodium carbonate and potassium carbonate can also be used arbitrarily at high temperatures. In various embodiments, the alkaline material comprises one or more of the following: a caustic exchange resin (eg, a sulfonium ion exchange resin): ammonia or ammonium hydroxide; an alkaline clay such as limestone, dolomite, magnesite, sepiolite And olivine: activated carbon and/or impregnated activated carbon; anion exchange resin such as styrene-divinylbenzene polymer backbone from -27 to 201235334 and selected from -N(CH3) 2, -NRH or -NR2 a weakly basic ion exchange resin of the amine functional structure wherein R is hydrogen or an alkyl group having from 1 to 20 carbon atoms; an amine polyoxyalkylene functionalized with ethylenediamine; grafted in a microporous or interstitial pore Organic alkaline materials on metallic oxides: other organic-inorganic solids such as zeolites exchanged with metals selected from the group consisting of lithium, sodium, potassium, rubidium, calcium, strontium, barium and radium: utilizing selected from lithium and potassium , sodium, antimony and metal-treated oxides of Group III of the Periodic Table of the Elements; supported or solid alkalis, alkaline earth metals or organometallics; usually derived from the interaction of magnesium salts and soluble citrates Magnesium sulphate: salt with alkaline hydrolysis Sodium acetate, sodium bicarbonate, sodium phenolate and sodium carbonate; and amines such as primary, secondary or tertiary aliphatic or aromatic amines, such as aniline, n-butylamine, heterocyclic amines such as pyridine, piperidine , piperazine, triethylamine, aliphatic or aromatic diamines, and alkanolamines. In particular, amines in the form of their salts with weak organic acids can be used. Conveniently, the basic material is a diamine such as 2-methyl pentamethylamine or hexamethylenediamine, which is commercially available from Invista S. & rl Corporation under the trade name DYTEKtm A and DYTEKtm HMD. Suitable solid alkaline materials include: alkaline metal oxides; bismuth on metal oxides; alkaline earths on metal oxides; alkali and alkaline earth zeolites: transition metal rare earths and higher valence oxides; hydrotalcites, sintered Hydrotalcites and spinels, in particular hydrotalcites selected from the group consisting of lithium, potassium, sodium, cesium, alkali metal and combinations thereof; perovskites; and /3-alumina. In one embodiment, the basic material is one or more of the hindered amines described in U.S. Patent No. 6,201,157. It will be appreciated that the alkaline material may be added in an anhydrous state from -28 to 201235334 or may be an aqueous solution of any of the foregoing alkaline materials (particularly the metal hydroxide or a salt having an alkaline hydrolysis). 'The liquid basic material used in the neutralization reaction of the present invention (such as the amine or diamine discussed) has a relatively low volatility and a normal boiling temperature higher than the normal boiling temperature of cyclohexylbenzene to make the material easy Residue in the bottoms product in a subsequent fractionation operation, the fractionation operation can be carried out on at least a portion of the treated cracking reaction product which can contain such liquid alkaline material. The conditions for the neutralization reaction vary with the acid catalyst and alkaline material utilized. Suitable intermediate conditions include at least 3 01, or at least 40 ° C, or at least 50 ° C, or at least 60 ° C, or at least 70 ° C, or at least 80. (:, or at least 90 ° C. Other suitable conditions include no more than 2 〇〇. 〇, or not higher than 190 ° C, or not higher than 180 ° C, or not higher than I70t, Or not at 160 ° C, or not higher than 150 ° C, or not higher than 14 〇 t:, or not higher than 130 ° C, or not higher than 120. (:, or not higher than 11 〇 t, Or a temperature not higher than 1 〇〇 ° C. In various embodiments, the neutralization condition includes a temperature that is lower than the cleavage reaction condition', for example, the temperature may be 1 ° C lower than the temperature of the cleavage reaction, or 5 ° C , or 10 ° C, or 15 ° C, or 2 01, or 30 °, or 40 ° C. Suitable neutral conditions can range from about 1 psig to about 500 psig (5 kPa gauge to 3450 kPa gauge) ), or a pressure of from about 10 pSig to about 200 pSig (7 〇 kP a gauge to 1380 kP a gauge) such that the treated cleavage reaction mixture is completely or predominantly in the liquid phase during the neutralization reaction -29- 201235334 After neutralization, the neutralized acid product can be removed from the cleavage product, leaving a crude mixture of phenol and cyclohexanone, which can be purified by methods well known in the art and Minute The invention will now be more particularly described with reference to the accompanying drawings in which FIG. 1 is a flow diagram of a general method of treating a hydrogenation reaction product of benzene, but FIG. 2 is a process according to a first example of the present invention. Flowchart of a method for producing a product. Referring to Figure 1, in this general method, a product of a benzene hydroalkylation reaction comprising cyclohexylbenzene, one or more polycyclohexylbenzenes, and unreacted benzene is sent via line 11 to a first fractionation column 12. The reaction product is supplied to the column at a temperature of from about 120 ° C to about 140 ° C and at a point near the bottom of the column when it enters the column 12. At its upper end, The column 12 is connected to a vacuum source 13 such that the column 12 is typically operated at a pressure of from about 20 kPa to about 50 kPa. On the bottom near the column 12, the substream 14 can be removed from the column by heating The reactor 15 is recycled to the column such that the temperature at the bottom of the column 12 is typically between about 20 (TC to about 24 1 ° C. The benzene hydroalkylation product is fractionated in the column 12 to prepare C6 fraction rich in unreacted benzene and rich in cyclohexylbenzene, polycyclohexylbenzenes and other heavy metals C12 + fraction. This (6 fraction is removed from the upper end of the column 12 via line 40 with the aid of the vacuum source 13 and can be recycled, in whole or in part, via line 16 to the hydrogen of the benzene. An alkylation reactor (not shown). This stream in a portion of line 40 can be partially recycled to the column 12 as a reflux stream 17 and can be partially sent to the transalkylation via line 18. Reactor 19. The C, 2+ fraction is removed from the column i 2 -30-201235334 via line 2 1 and supplied to the second fractionation column 22. The upper end of the second column 22 is connected to a vacuum source 23 such that the column 22 is typically operated at a pressure of from about 10 kPa to about 20 kPa. Additionally, the side stream 24 can be removed from near the bottom of the column 22 and can pass through the heater 25 before being recycled to the column 22 such that the temperature profile at the bottom of the column 22 is between about 220 ° C and about 241. Between °C. The C12+ fraction is split in the column 22 into a top fraction rich in cyclohexylbenzene via line 41 and a bottom fraction rich in polycyclohexylbenzene via line 27. The overhead fraction of one portion of line 41 is removed via line 26 for additional treatment of the cyclohexylbenzene, but the bottoms fraction is supplied to third fractionation column 28 via line 27. A portion of the stream in line 41 can be recycled to column 22 as reflux stream 42. The third column 28 is connected at its upper end to a high vacuum source 29 such that the column 28 typically operates at a pressure of from about 1 kP a to about 10 kPa. Additionally, substream 31 is removed near the bottom of column 28 and passed through heater 32 prior to being circulated to column 28 such that the temperature at the bottom of column 28 is typically between about 22 (TC to about 24 1 °C). The column 28 will fractionate the overhead fraction from the column 22 via line 43 to a first fraction rich in polycyclohexylbenzene (which is supplied via line 33 to the transalkylation reactor 1 9 ) And a heavy fraction removed for removal or supply as a fuel via line 34. A portion of the stream in line 43 can be recycled to column 28 as a reflux stream 44 ° in line 33 Cyclohexylbenzenes are reacted with benzene from line 18 in the transalkylation reactor 19 to produce a transalkylation reaction effluent -31 - 201235334 'The effluent contains predominantly cyclohexylbenzene and unreacted benzene, And returning to the first fractionation column 12 via line 35. Referring now to Figure 2, in the process according to the invention, the hydroalkylation reaction product is again sent to the first fractionation column 111, in this case via line 112. Again, the substream 113 can be removed near the bottom of the tower 111, through the heater 114 and Circulation to the column. However, in addition, the benzene recovered from the top of the column 111 via line 129 is preheated in another heater 115 and evaporated and injected into the bottom of the column 111 via line 116. In this manner, pressurized The steam heats the recycled benzene, and the temperature at the bottom of the column 111 can be easily maintained between about 190 ° C and about 241 ° C. At this temperature, even if the column is at atmospheric pressure or Operating at a pressure above atmospheric pressure (100 kPa to 3 kPa), substantially all of the Cl2 and lower hydrocarbon components are in the vapor phase at the bottom of the column 111. Thus, the liquid bottom stream leaving the column 111 It is mainly composed of polycyclohexylbenzenes and other heavy products and can be directly sent to the transalkylation reactor 1 18 via line 117. At or slightly above the point of the column 111, the liquid tributary can be The column 111 is removed and sent to the second fractionation column 121 via line 119. Since the side stream is substantially free of C18+ hydrocarbons, the column 121 can be operated above atmospheric pressure (typically between 105 kPa and 110 kPa) to Dividing the substream into a bottom stream of cyclohexylbenzene and a top of the benzene rich The bottom stream of the cyclohexylbenzene can be recovered via line 22 for additional processing, but the benzene-rich overhead stream can be returned to the column 1 1 1 via line 1 2 3. To aid in the column 1 For the separation of benzene and cyclohexylbenzene, the side stream can be removed, for example, from the position of the line 1 23 via line 1 24 from line 1 1 1 -32 - 201235334 and passed through cooler 125 before returning to column 111. The gas phase overhead exiting the column via line 126 consists essentially entirely of (C6-) impurities. The top initially passes through condenser 127 where light impurities are removed for use as fuel and the benzene is condensed prior to passage to the evaporation unit. The benzene can be heated in the unit 128 and re-evaporated to the benzene vapor at least partially via line 1 29 to the heater for partial delivery to the hydrogenation unit via line 131 (not shown via line 132) Sent to the transalkylation reactor 1 18. The benzene vapor from line 132 and the polyphenyls (both di- and tricyclohexylbenzene) at the bottom of column 11 1 should be produced in the transalkylation reactor 11 Cyclohexylbenzene. The transalkylation reactor 118 can be sent to a third fractionation column 134 via line 133, wherein unreacted C24+) hydrocarbons are removed via bottom line 135 for removal and the benzene-rich gas phase is passed via The overhead line 136 is removed and sent to the first fractionation column for operation of the third fractionation column 134 at atmospheric pressure and a low bottom temperature of about 22 (TC to about 2411), heated benzene vapor from the heater 1 15 It can be supplied to the column 134 via line 137. Although the invention has been described and illustrated with reference to the particular embodiments thereof, those skilled in the art will appreciate that the invention may be modified herein. For this reason, reference should be made only to the scope of the appended claims. [Simple diagram] The mode, benzene and light of the 128, and 115, and the weight of the reverse effluent in the cyclohexyl group 8 (cyclohexyl 111) (the bottom of the typical part is as good as the description -33- 201235334 Figure 1 is a flow diagram of a process generally used to treat the alkylation reaction product of benzene. Figure 2 is a flow diagram of a process for treating the alkylation reaction product of benzene in accordance with a first example of the present invention. [Main component symbol description] 11,16,18,21,26, 27, 3 3,34,40,41,43,112,116, 117,119,122,123,124,126,1 29, 1 3 1, 1 3 2, 1 3 3, 1 3 5, 1 3 6,1 3 7 : Line 12, 1 1 1 : First fractionation column 13, 23: Vacuum source 14, 24, 31, 113: Branch 15 , 25, 1 14,1 15 : heater 17, 44 : reflux stream 19.1 1 8 : transalkylation reactor 22, 121: second fractionation column 28, 134: third fractionation column 29: high vacuum Source 125: cooler 127: condenser 128: evaporation unit - 34-