200406379 玖、發明說明： 【發明所屬之技術領域] 本务明係關於藉由氧或含氧的氣體將烴氧化為相應的羧 酸、醇及/或_，或將醇、及/或_氧化為相應的羧酸。 【先前技術】 〃在催化劑的存在下，藉由烴的氧，特別是環㈣，直接 氧化之方法’已研究相當長一段時間。這是因為在避免使 用目月ίι工業衣私上用於其中一階段如硝酸之氧化劑，是明 顯有利的，而可省去處理其所產生的氧化氮。 /在以氧作為催化氧化方法之許多選擇的形式中，鈷是最 苇建議使用的催化劑。 口此λ開於1940年十二月的美國專利案uS-A_2 223 493 ，揭示了在一通常包含醋酸的液相中，於至少6〇它的溫度 下，使用一含氧的氣體及在氧化催化劑（如鈷化物）的存在下 ’將環烴類氧化為相應的二酸。 公開於1990年二月的美國專利案US-A-4 902 827,揭示了 一在包含醋酸的液相中，於至少8〇t到16〇t的溫度下，及 在包3可洛性鈷化物及一可溶性锆化物或銓化物的氧化 催化背！存在下，將環己貌的氣體氧化為己二酸的改良。 表L在美國專利案ΕΡ-Α-0 694 333用氧的烴氧化中，已 建礒使用包含一鈷鹽及一鐵鹽之催化劑。 在美國專利案Ep 〇 87〇 751令建議使用包含一鈷鹽及一 路鹽之催化劑以增進其選擇性。 鎂可作為本氧化反 應之另外習用催化劑。 85274 200406379 【發明内容】 然而’結果是，當伟田上^ 田便用則述之先前技術的催化系統所獲 得的選擇性和生彦產吾炎π 4 / 座屋里為可接受時，可增進生產產量及選 擇性並且催化劑宏I m % u < t d合易口收及再利用之新穎的催化系統，總 是所欲的。 迈就疋本發明所希望達成的。本發明更特別包含在液相 中及催4b y存在下’使用氧或含氧的氣體對烴、醇及，或酌 之氧化方法’其特徵為該催化劑包含至少一錯化物及至少 一#化物。 於本發明之方法中作為起始物質之煙，特別為具有3至2〇 個碳原子之烷烴、環烷烴、芳香烷烴、烯烴及環烯烴。 在該等烴類中，特別是那些具有5至12個碳之環烧煙為最 重要，因為其氧化產生了羧酸或中間環醇及環酮。 最佳的烴為環己烷，其氧化所產生的己二酸為聚醒胺_6,6 之基本化合物之一，並且亦可提供環己_，產生己内醯胺 ’因而產生聚醯胺_6,6。 本發明方法亦可用作中間醇類或酮類之氧化，特別是具 有5到12個碳原子之環烷醇及環烷酮，例如環己酮及/或環 己醇’以製備相應的二魏酸。 以下，本方法將會特別描述煙之氧化，基本上為環烷烴 ’較佳為環己烷之氧化。 【實施方式】 包含锆化物及鈽化物的催化系統使得氧化環己产直接⑽ 備具有良好選擇性的己二酸變成可能。這此 " 〜‘ m化性質對力 85274 200406379 忒氧化反應之工業上操作，為明顯高度有利的。 根據本發明第一實施例，該催化系統包含至少一可溶於 :應介質(reaction medium)之錘化物’例如，係選自(非限' 定)氯化锆、溴化錯、硝酸鍅、乙醯丙酮酸鍅及羧酸錘，如 四水醋酸結、丙酸鍅、己二酸錘、戊二酸錯、琥梅或 辛酸錯’及至少-可溶於反應介f (r㈣tiGn 之錦化 物，例如，係選自（非限定）a化飾、漠化錦、硝酸錦、乙 醯丙酮酸鈽及羧酸鈽，如四水醋酸鈽、丙酸鈽、己二酸鈽 、戊二酸鈽、琥珀酸鈽或辛酸錦。 % 該催化劑亦可包含其他金屬化合物作為添補元素Η— element)，其係選自下列各物組成之群：銅（Cu)、銀（Ag) 、金（Au)、鎂（Mg)、鈣（Ca)、锶（Sr)、鋇（Ba)、辞（Zn)、鎘 (Cd)、水（Hg)、鋁（A1)、銳（Sc)、銦（In)、蛇（τι)、紀（γ)、 鎵（Ga)、鈦（Ti)、給（Hf)、鍺（Ge)、錫（Sn)、錯（pb)、凱（v) 、鈮（Nb)、鈕（Ta)、鉻（Cr)、翻（Mo)、鎢（W)、錳（Μη)、鉻 (Tc)、銖（Re)、鐵（Fe)、釕（Ru)、鐵（〇s)、始（c〇)、姥（灿）籲 、銀（Ir)、鎳（Ni)、鈀（Pd)、鉑（Pt)及該等化合物之組合。術 語「金屬元素化合物」，係指包含至少一該金屬元素與其他 化學元素（例如，氧）化合之化合物，。 根據本發明第二實施例，符合本發明之催化劑包含一含 有至少一鍅化物及至少一鈽化物之載體（support)。根據製 造載體催化劑之習知技術，該鍅化物及鈽化物為承載或置 於堕性的載體上。該催化劑亦可包含鍅及鈽氧化物的混合 物或是混合錯氧化物及鈽氧化物之混合物。該催化劑亦可 85274 200406379 包含一或多個如上述第一實施例之金屬元素化合物，作為 添補元素。 本發明適合的金屬氧化物載體，有利的為多孔性（p〇r〇us) 金屬氧化物，例如銘氧化物化或矽氧化物、石墨或活性碳 、沸石（zeolite)、矽酸鹽、磷酸鋁、磷酸矽鋁或有機樹脂。 鍅和鈽的莫耳比例可廣泛變化。可用的莫耳比例為介於 1/0.00001及1/100之間，較佳的為介於1/〇〇〇〇1及1/1〇之間。 其他金屬的量（當其存在時）與錘的莫耳比，則與上述的鈽 相似。 藉由至入锆及鈽化物，且視需要可置入其他金屬的化合 物’於反應介質中，可在原位得到該催化劑。藉由混合所 需比例的該化合物，而得到锆對錦及其他金屬（視需要）的莫 耳比，亦可即席製備該催化劑。 此此合物較佳的是利用與使用於氧化反應中相同性質之 有利的溶劑來製備。 催化劑的量是以金屬元素（錯、飾，視需要，及其他金 消於反應混合物的重量百分比來表示，-般介於0·剛 2之間’有利的為介於0侧及2%之間，但這些數值並 ，要：:，、'而，不需要使用過多的量’而就能有良好的活 離其乃’催化劑必須從最終的反應介質中 二::化氧=發氧化反應亦是㈣^ 基過氧化氫。例如環己基過氧化氫或是第三 、’、可為酮類或醛類，例如，環己酮，其 85274 200406379 環己烧氧化中所形成的化合物之一，或乙醛。一般而言， 引舍劑為所用的反應介貝重里之0. 〇 1 %至2 〇 %重量比，這些 比例數值並不重要。引發劑之使用特別是用在氧化引發反 應期間及當環己烷的氧化在低於12〇t溫度下進行時，以及 其分別作用時。引發劑可在反應開始時就導入。 該液相反應介質較佳的包含一至少為執行本發明方法製 備目彳示之煙及/或醇及/或酮之部分溶劑。該溶劑本質可非常 多樣化，其在反應的條件下為幾乎完全不可氧化。該溶劑 特別可選自極性質子溶劑及極性非質子溶劑。就極性質子 溶劑而言，例如，只具有一級或二級氫原子之羧酸的極性 質子溶劑，特別是具有2到9個碳原子之脂鏈烴酸（aliphatic aCld)，如醋酸，全氟烷基羧酸（Perfluoroalkykarboxylic acid) ’如二氟醋酸’親脂性（lipophilic)酸，如己酸、庚酸、辛 酸、2 -乙基己酸、壬酸、癸酸、十一酸、十二酸、硬脂酸（ 十八酸）及其全曱基化衍生物（亞曱基團上的氫被甲基完全 取代）、2-十八烷基丁二酸、2，5-二（第三丁基）苯甲酸、4_( 第二丁基）苯甲酸、4_辛基苯甲酸、第三丁基氫正鄰苯二甲 酸（tert-butyl hydrogen orthophalate)、經烧基取代之環烧酸 (naphthenic)或恩酸（anthracenic acid)，較佳為第三 丁基型 ’鄰苯二曱酸之取代衍生物或脂肪酸，如脂肪酸二聚物。 就酸而言’屬於前述之族及帶有不同予體電子（electr〇n d〇nating)取代基、或電子收回（electron-withdrawing)取代基 (iS素石尹、醯亞胺（sulphonimides)、石肖基或石黃酸根基團或其 類似物）、或醇類，如第三丁醇。就極性非質子溶劑而言， 85274 200406379 例如羧酸之低烷基酯類之極性非質子溶劑（低烷基係指，具 有1到4個碳原子之烷基自由基）’特別是上述的羧酸、四亞 甲基砜（或環丁砜）、亞硝酸鹽、酮類，如丙酮、或鹵化煙， 如，一氣甲烧、氯苯、二氯苯或氟化煙。 作為環己烷氧化反應之溶劑，較佳為具有親脂性或非親 脂性之羧酸。方便應用催化劑，其鍅及鈽取代基之化合物 形式係衍生自作為溶劑之羧酸或氧化反應所產生的酸，在 此情況下該化合物可溶於反應介質中。 上述定義之溶劑一般而言為反應介質之1%到99%重量比 ’較佳的為5%到90%，更佳的為1 〇%到如％。 導入。 氧化亦可在水存在下進行，水可在起始階段或反應期間 特別是根據所使用的物 間’較佳的為介於8〇艺 氧化反應可在各種溫度下進行，特 質而定。一般是介於5〇t：和200°C之間 和140°C之間。200406379 发明, Description of the invention: [Technical field to which the invention belongs] The present invention relates to the oxidation of hydrocarbons to the corresponding carboxylic acids, alcohols and / or _, or the oxidation of alcohols and / or _ by means of oxygen or oxygen-containing gases Is the corresponding carboxylic acid. [Prior art] The method of direct oxidation of rhenium in the presence of a catalyst, especially by cyclooxygenation of hydrocarbons, has been studied for a long time. This is because it is obviously advantageous to avoid the use of oxidants such as nitric acid in one stage of industrial clothing privately, and the treatment of the nitrogen oxides produced by them can be omitted. / Among the many options for catalytic oxidation with oxygen, cobalt is the most recommended catalyst. The U.S. patent No. uS-A_2 223 493, published in December 1940, discloses the use of an oxygen-containing gas in a liquid phase usually containing acetic acid at a temperature of at least 60 ° C and oxidation. The presence of a catalyst (such as a cobalt compound) 'oxidizes cyclic hydrocarbons to the corresponding diacid. U.S. Patent No. US-A-4 902 827, published in February 1990, discloses a solution containing acetic acid at a temperature of at least 80 to 160 t, Oxidation of a compound and a soluble zirconium or hafnium compound! Improvement of oxidation of cyclohexyl gas to adipic acid in the presence. Table L In the U.S. patent case EP-A-0 694 333 for the oxidation of hydrocarbons with oxygen, it has been proposed to use a catalyst comprising a cobalt salt and an iron salt. In U.S. Patent No. Ep 87 0 751, the use of a catalyst containing a cobalt salt and a way salt is suggested to enhance its selectivity. Magnesium can be used as another conventional catalyst for this oxidation reaction. 85274 200406379 [Summary of the invention] However, 'the result is that when Wei Tian Shang ^ Tian Bian used the catalytic system of the prior art to obtain the selectivity and the production of Yan Yan Wu Wu π 4 / in the house can be improved, It is always desirable to produce a novel catalytic system with a yield and selectivity, and a catalyst macro I m% u < td that can be easily taken in and reused. Step into what the present invention hopes to achieve. The present invention more particularly includes 'using oxygen or an oxygen-containing gas to hydrocarbons, alcohols, and / or an optional oxidation method' in the liquid phase and in the presence of the catalyst, characterized in that the catalyst contains at least one complex and at least one compound . The smoke used as the starting material in the method of the present invention is particularly an alkane, a cycloalkane, an aromatic alkane, an olefin, and a cyclic olefin having 3 to 20 carbon atoms. Of these hydrocarbons, especially those with 5 to 12 carbon rings are the most important because their oxidation produces carboxylic acids or intermediate cyclic alcohols and cyclic ketones. The best hydrocarbon is cyclohexane, and the adipic acid produced by its oxidation is one of the basic compounds of polyamine-6,6, and it can also provide cyclohexanone to produce caprolactam 'and thus polyamine. _6,6. The method of the present invention can also be used for the oxidation of intermediate alcohols or ketones, especially cycloalkanols and cycloalkanones having 5 to 12 carbon atoms, such as cyclohexanone and / or cyclohexanol 'to prepare the corresponding two Wei acid. In the following, the method will specifically describe the oxidation of smoke, which is basically the oxidation of cycloalkanes, preferably cyclohexane. [Embodiment] A catalytic system including a zirconium compound and a hafnium compound makes it possible to directly produce adipic acid with good selectivity from oxidized cyclohexane. These " ~ 'm chemical properties are obviously highly advantageous for the industrial operation of the force 85274 200406379 tritium oxidation reaction. According to a first embodiment of the present invention, the catalytic system includes at least one hammer compound that is soluble in a reaction medium (for example, selected from (non-limiting) zirconium chloride, bromide, hafnium nitrate, Acetylpyruvate and carboxylic acid hammers, such as acetic acid tetrahydrate, hydrazone propionate, adipic acid hammer, glutaric acid, succinic acid or octanoic acid 'and at least-soluble in the reaction medium f (r㈣tiGn) For example, it is selected from (non-limiting) a chemical decoration, desertification brocade, nitrate bromide, acetamidine pyruvate, and carboxylate, such as acetic acid tetrahydrate, propionate, adipic acid, glutaric acid, etc. , Osmium succinate or caprylic acid.% The catalyst may also contain other metal compounds as supplementary element Η—element), which is selected from the group consisting of copper (Cu), silver (Ag), and gold (Au) , Magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), rhenium (Zn), cadmium (Cd), water (Hg), aluminum (A1), sharp (Sc), indium (In) , Snake (τι), Period (γ), Gallium (Ga), Titanium (Ti), Feed (Hf), Germanium (Ge), Tin (Sn), W (pb), Kai (v), Niobium (Nb) , Button (Ta), Chromium (Cr), Turn (Mo), Tungsten (W), Manganese (Μη), chromium (Tc), baht (Re), iron (Fe), ruthenium (Ru), iron (0s), beginning (c0), hafnium (Can), silver (Ir), nickel (Ni ), Palladium (Pd), platinum (Pt) and combinations of these compounds. The term "metal element compound" means a compound containing at least one metal element combined with other chemical elements (for example, oxygen). According to a second embodiment of the present invention, a catalyst according to the present invention includes a support including at least one halide and at least one halide. According to the conventional technology for producing a supported catalyst, the halide and the halide are carried or placed on a degraded carrier. The catalyst may also include a mixture of rhenium and rhenium oxide or a mixture of mixed oxides and rhenium oxide. The catalyst 85274 200406379 may also contain one or more metal element compounds as the above-mentioned first embodiment as a supplemental element. The suitable metal oxide support of the present invention is advantageously a porous metal oxide, such as oxidized or silicon oxide, graphite or activated carbon, zeolite, silicate, aluminum phosphate , Silicon aluminum phosphate or organic resin. The mole ratio of and 钸 can vary widely. The usable mole ratio is between 1 / 0.00001 and 1/100, and preferably between 1/0001 and 1/1. The amounts of other metals (when they are present) and the molar ratio of the hammer are similar to those of 钸 above. The catalyst can be obtained in situ by introducing zirconium and hafnium compounds and, if necessary, compounds of other metals' into the reaction medium. The catalyst can also be prepared on the fly by mixing the compound in the required ratio to obtain a molar ratio of zirconium to brocade and other metals (as needed). This compound is preferably prepared using a favorable solvent having the same properties as those used in the oxidation reaction. The amount of catalyst is expressed by the weight percentage of metal elements (wrong, decorative, as needed, and other gold consumed in the reaction mixture,-generally between 0 · 2 and 2 ', advantageously between 0 and 2%). However, these values do not need to be :: ,, 'and, without using too much amount' to have good activity, the catalyst must be removed from the final reaction medium. 2 :: oxygenation = oxidation reaction It is also ㈣ ^ -based hydrogen peroxide. For example, cyclohexyl hydrogen peroxide or the third, ', may be ketones or aldehydes, for example, cyclohexanone, one of the compounds formed in the oxidation of cyclohexanone 85274 200406379 Or acetaldehyde. Generally speaking, the starting agent is from 0.01% to 20% by weight of the reaction medium used. These proportions are not important. The use of initiators is particularly used to initiate the reaction by oxidation. During and when the oxidation of cyclohexane is performed at a temperature lower than 120 t, and when it is separately acting. The initiator can be introduced at the beginning of the reaction. The liquid-phase reaction medium preferably contains at least one for carrying out the invention Method for preparing smoke and / or alcohol and / or ketone fraction as shown Solvents. The nature of the solvents can be very diverse, and they are almost completely non-oxidizable under the conditions of the reaction. The solvents can be particularly selected from polar protic solvents and polar aprotic solvents. For polar protic solvents, for example, only Polar protic solvents for carboxylic acids of primary or secondary hydrogen atoms, especially aliphatic aCld with 2 to 9 carbon atoms, such as acetic acid, Perfluoroalkykarboxylic acid Fluoroacetic acid 'lipophilic acids such as hexanoic acid, heptanoic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, undecanoic acid, dodecanoic acid, stearic acid (octadecanoic acid), and Perfluorinated derivatives (the hydrogen on the fluorenyl group is completely substituted by methyl), 2-octadecylsuccinic acid, 2,5-bis (third butyl) benzoic acid, 4_ (second butyl Benzoic acid, 4-octyl benzoic acid, tert-butyl hydrogen orthophalate, naphthenic or anthracenic acid substituted with alkyl groups, compared with It is preferably a substituted derivative or fatty acid of the third butyl type phthalic acid, such as a lipid Acid dimers. As far as acids are concerned, they belong to the aforementioned group and have different electron-substituting substituents or electron-withdrawing substituents (iS Su Shiyin, 醯 imine). (Sulphonimides), schottky or luteinate groups or the like), or alcohols such as tertiary butanol. For polar aprotic solvents, 85274 200406379 polar aprotic such as low alkyl esters of carboxylic acids Solvent (low alkyl means an alkyl radical having 1 to 4 carbon atoms) 'especially the aforementioned carboxylic acids, tetramethylene sulfone (or sulfolane), nitrites, ketones such as acetone, or Halogenated fumes, such as methane, chlorobenzene, dichlorobenzene or fluorinated fumes. As a solvent for the cyclohexane oxidation reaction, a carboxylic acid having a lipophilic or non-lipophilic property is preferable. Convenient to use catalysts, the compound form of the fluorene and fluorene substituents is derived from a carboxylic acid as a solvent or an acid produced by an oxidation reaction, in which case the compound is soluble in the reaction medium. The solvent as defined above is generally 1% to 99% by weight of the reaction medium, preferably 5% to 90%, and more preferably 10% to 100%. Import. Oxidation can also be carried out in the presence of water. Water can be used in the initial stage or during the reaction, especially depending on the material used. It is preferably between 80 ° C. The oxidation reaction can be carried out at various temperatures, depending on the nature. It is generally between 50 ° C and 200 ° C and between 140 ° C.
以下列實例說明本發明。 實例1The following examples illustrate the invention. Example 1
-22·4 g的環己烷 85274 200406379 -27·3 g的醋酸 -0.22g的環己_ 1 g的催化劑（係將氧化錯及氧化鈽充置於氧化链上所形 成的，在反應介質中使其能有7370 ppm的鈽及6700 ppm的鍅） 關上反應器後，以搖晃攪拌將混合物加熱至l〇5t。反應18〇 分鐘後’將蒸氣壓力鍋冷卻然後去除氣體。 分析該反應混 a物以測彳于轉化的程度及選擇性。以氣相層析法進行分析。 術浯「選擇性（ST)」，以百分比表示，係指定量測得之全 部莫耳數相對於由實際轉化的環己烷計算得來之理論上全 部的莫耳數之莫耳比。 所得到的結果如下： -環己烷的轉化程度（DC): 5.5% -環己醇相對於轉化環己烷之選擇性（ST): 24.6% •環己酮相對於轉化環己烷之選擇性（ST): 1.3% •己二酸相對於轉化環己烷之選擇性（ST): 51.4% -己二酸/所形成全部二酸之莫耳比： 80.8% 於相同的設備及相同的操作條件下，以下列反應物，重 複實例1 : -22_ 1 g的環己烧 -27.2 g的醋酸 -〇·22 g的環己酮 -〇·49 g的乙醯丙酮酸鍅，使其能有186〇 ppm的锆於反應 介質中。 85274 -12- 200406379 反應時間為180分鐘及反應溫度為105它。 所得到的結果如下： -環己烷的轉化程度（DC): 4.4% -環己醇相對於轉化環己烷之選擇性（ST): 28.4% -環己酿]相對於轉化環己烷之選擇性（ST): 45.1% -己二酸相對於轉化環己烷之選擇性（ST): 9.2% -己二酸/所形成全部二酸之莫耳比： 實例3 56.4% 於相同的設備及相同的操作條件下，以下列反應物，重 複實例1 : _22·5 g的環己烷 -27·5 g的醋酸 -0·24 g的環己酮 -0·43 g的乙醯丙酮酸錯及〇i6i6g的丙酮酸筛，使其能有 1600 ppm的鍅及1320 ppm的筛於反應介質中 反應時間為1 8 0分鐘及反應溫度為1 〇 5。 所得到的結果如下： 〇 -環己烷的轉化程度（DC) ·· 2.5% -環己醇相對於轉化環己烷之選擇性（ST): 16.2% -環己酮相對於轉化環己烷之選擇性（ST): 0% -己二酸相對於轉化環己烷之選擇性: 27.9% 與實例2相比，本試驗顯示，藉由銼進行己二酸催化作用 之選擇性，在鈽存在下有正面效果。 85274 -13 --22 · 4 g of cyclohexane 85274 200406379 -27 · 3 g of acetic acid-0.22 g of cyclohexyl_ 1 g of catalyst (formed by filling the oxidation chain and thorium oxide on the oxidation chain in the reaction medium (7370 ppm 钸 and 6700 ppm 鍅) after closing the reactor, the mixture was heated to 105 t with shaking and stirring. After 18 minutes of reaction, the steam pressure cooker was cooled and the gas was removed. The reaction mixture was analyzed to determine the extent and selectivity of the conversion. Analysis was performed by gas chromatography. The term "selectivity (ST)", expressed as a percentage, is the molar ratio of the total molar number measured in a specified quantity to the theoretical total molar number calculated from the actually converted cyclohexane. The results obtained are as follows:-Degree of cyclohexane conversion (DC): 5.5%-Selectivity of cyclohexanol relative to cyclohexane (ST): 24.6% • Choice of cyclohexanone relative to cyclohexane (ST): 1.3% • Selectivity of adipic acid to cyclohexane (ST): 51.4% -Molar ratio of adipic acid / total diacids formed: 80.8% on the same equipment and the same Under the operating conditions, Example 1 was repeated with the following reactants: -22_ 1 g of cyclohexanone-27.2 g of acetic acid-0.22 g of cyclohexanone-0.49 g of acetamidine pyruvate There was 1860 ppm of zirconium in the reaction medium. 85274 -12- 200406379 The reaction time is 180 minutes and the reaction temperature is 105 ° C. The results obtained are as follows:-Degree of conversion of cyclohexane (DC): 4.4%-Selectivity of cyclohexanol relative to converted cyclohexane (ST): 28.4%-Cyclohexane] Selectivity (ST): 45.1%-Selectivity of adipic acid to cyclohexane (ST): 9.2%-Molar ratio of adipic acid / total diacids formed: Example 3 56.4% in the same equipment Under the same operating conditions, Example 1 was repeated with the following reactants: _22 · 5 g of cyclohexane-27 · 5 g of acetic acid-0 · 24 g of cyclohexanone-0 · 43 g of acetamidinepyruvic acid Mismatched with 0,6,6 g of pyruvate sieve so that it can have 1,600 ppm of rhenium and 1,320 ppm of sieve in the reaction medium with a reaction time of 180 minutes and a reaction temperature of 105. The results obtained are as follows: 〇-Cyclohexane conversion (DC) 2.5%-Selectivity of cyclohexanol relative to converted cyclohexane (ST): 16.2%-Cyclohexanone relative to converted cyclohexane Selectivity (ST): 0%-Selectivity of adipic acid relative to converted cyclohexane: 27.9% Compared with Example 2, this test shows that the selectivity of adipic acid catalysis by file is There are positive effects in the presence. 85274 -13-