201235343 六、發明說明： 【發明所屬之技術領域】 本％明係有關於氣態盼與含特定量稀 氫化反應以製造環己酮之方法。 釋氣版之氫氣進行 【先前技術】 環己_乃生成己内酿胺時所需要的〜 醯月女則為形成耐論-6的重要單體。工 ]物而己ί201235343 VI. Description of the invention: [Technical field to which the invention pertains] This is a method for producing a cyclohexanone by a gaseous reaction with a specific amount of a dilute hydrogenation reaction. The gas released from the gas release version [Prior Art] Cyclohexyl amide is required for the formation of caprolactam ~ 醯月女 is an important monomer for the formation of resistance to -6. Work]
多經由環己錄化反應或是g分氫化反應己_的製備; 化反應需要較嚴苛之反應條件，且會生：广經由環己烷， 副產物，造成反應的轉化率及環己购"^已醇或有機酸= 對於工業上之製備會有耗能及分離複雜自偏低’所1 氫化反應製備環己酮之方法，其可區分為問題。至於利用g 生成環己酮的-步法以及經由中間物〗 為起始物直# 酉同的二步法。相較之下，㈣直接生己醇取終生成環€ 长已S同的一步法斜$ 工業上能量及成本的損耗具有明顯優勢之产乃在於一+ 中為了進行環己醇去氫反應必須料大量熱能=且一= 之反應可選擇在液態或是氣態中進行。 而在紛-步法製備環己酮的過程中，會有環己醇以及各種 不同之田J產物生成’故在此製程方法中許多純化的步驟及方 法衍然而生。如：WO 2009/131769 Al、wo 2009/080618 A1 及WO 2009/080620 A1等專利公開案中揭示利用酚氫化製 備環己酮的多重次蒸餾製程方法及純化步驟。另外，美國專 TF1004507 3 201235343 利US 4,410,741中揭示一批次反應中利用鎳觸媒與液離、_ 混合藉由控制溫度、壓力及反應器内氫氣與氮氣之比例產生 環己酮的製程方法。 然而’在前述專利文獻中’為了克服反應本身選擇性不佳 之缺點，必須於反應後端增加多重次之蒸餾製裎及純化牛 驟’或者必須藉由改善觸媒活性以提高產物之選擇性。 鑒於上述問題，本發明提出一種效率高、合乎經濟價值且 可解决商業應用上固有問題之紛氫化反應生成環己_產物 之方法，其於氣態盼氫化生成環己酮的製程中，利用氣體稀 釋反應所需氫氣之濃度，而可在維持反應高轉化率的同時提 尚產物中酮的選擇率。此外，本發明之方法亦可適用於不同 屬性之觸媒。 ° 【發明内容】 本發明之一目的係要提供—種製備環己酮之方法，其中可 克服或至少減低一或更多個習知製程所存在之缺點。 本發明之發明人發現，在酚氫化反應生成環己_之製程 中，藉由導入額外氣體稀釋氣氣濃度之步驟，可增加產能及 減少能量消耗。 根據本發明之一較佳實施方式，係在一反應設備中，加入 包含有至少一種具有催化活性之第1〇族金屬的觸媒’在溫 度約為150〜200°C及壓力為〇〜22 psig的條件下進行氮化反 應，而將酚轉變為環己酮。該反應設備包含有進料槽、預熱 TF1004507 4 201235343 段、汽化段、反應器、冷凝器及收集槽等裝置。反應初期將 進料槽加熱使反應物盼呈融熔態，利用定量泵輸送，經預熱 • 段將反應物酚預先汽化，之後與反應所需之氫氣及稀釋用之 氣體一併進入汽化段，最後以混合氣體之狀態進入反應器， 與其内部填充之觸媒進行氫化反應，反應生成之產物經過冷 凝器之後取樣收集。 本發明之上述製程中，總氣體濃度之氫氣與稀釋氣體莫耳 Φ 濃度比為0.1〜15之間，較佳為0.1〜4之間；該觸媒包含有 0.5〜1.0%的第10族金屬，且該第10族金屬係選自於鉑或 鈀，較佳為鈀；該氫化反應係於氫氣與酚莫耳濃度之比率介 於3〜8之間的條件下進行；以及該稀釋用之氣體較佳為氮 氣。 【實施方式】 以下藉由具體實施例進一步說明本發明之特點與功效，但 φ 其並非用來限制本發明之範疇。 根據前述本發明較佳實施方式，在各實施例各自的反應條 件下進行氫化反應，將酚轉變為環己酮。 一、氫氣濃度對反應結果之影響： 實施例 氫氣莫耳濃 轉化率 環己酮之 環己酮加環己醇之 度比（％) (%) 選擇率(％) 選擇率（％) 1 80 99.8 85.2 99.94 2 44 99.5 91.3 99.96 TF1004507 5 201235343 反應條件：每小時重量空間速度為1.5，氫對酚之莫耳比 為4，反應壓力為14.7psig。 實施例1與2之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當加入氫氣濃度比由80%降至 44%時，反應產物環己酮之選擇率由85.2%提升到91.3%， 而反應整體之轉化率及環己酮加環己醇的總量皆維持於 99.5%及 99.9%以上。 實施例 氫氣莫耳濃 轉化率 環己酮之 環己酮加環己醇之 度比（％) (%) 選擇率（％) 選擇率（％) 3 80 99.8 88.1 99.90 4 44 99.3 91.8 99.97 反應條件：每小時重量空間速度為1.5，氫對酚之莫耳比 為4，反應壓力為7.3 psig。 實施例3與4之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當加入氫氣濃度比由80%降至 44%時，反應產物之環己酮選擇率由88.1%提升到91.8%， 而反應整體之轉化率及環己酮加環己醇的總量皆維持於 99.3%及 99.9%以上。 TF1004507 6 201235343 實施例 氫氣莫耳濃 轉化率 環己酮之 環己酮加環己醇之 度比（％) (%) 選擇率(％) 選擇率（％) 5 60 99.5 91.1 99.96 6 44 98.5 93.2 99.96 反應條件：每小時重量空間速度為2.3，氫對酚之莫耳比 為4，反應壓力為7.3 psig。 實施例5與6之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當加入氫氣濃度比由60%降至 44%時，反應產物之環己酮選擇率由91.1%提升到93.2%， 而反應整體之轉化率及環己酮加環己醇的總量皆維持於 98.5%及 99.9%以上。 實施例 氫氣莫耳濃 度比（％) 轉化率 (%) 環己酮之 選擇率(％) 環己酮加環己醇之 選擇率（％) 7 80 95.32 91.22 99.95 8 60 99.72 94.51 99.96 9 55 99.64 95.35 99.96 10 52 99.64 95.76 99.96 11 44 99.63 96.35 99.94 反應條件：每小時重量空間速度為2，氫對酚之莫耳比為 4，反應壓力為14.7 psig。 實施例7至11之反應乃使用Johnson Matthey商用觸媒 TF1004507 7 201235343 (Type 355，含0.8% Pd)，當加入氫氣濃度比由80%降至 44%時，反應產物之環己酮選擇率由91.2%提升到96.4%， 而反應整體之轉化率及環己酮加環己醇的總量皆維持於 99%及99.9%以上。 實施例 氫氣莫耳濃 度比（％) 轉化率 (%) 環己酮之 選擇率（％) 環己酮加環己醇之 選擇率（％) 12 80 99.8 44.2 99.85 13 44 99.5 66.8 99.79 反應條件：每小時重量空間速度為1.5，氳對酚之莫耳比 為4，反應壓力為14.7 psig。 實施例12與13之反應乃使用BASF-547970商用觸媒（含 0.9% Pd)，當加入氫氣濃度比由80%降至44%時，反應產物 之環己酮選擇率由44.2%提升到66.8%，而反應整體之轉化 率及環己酮加環己醇的總量皆維持於99%及99.5%以上。 實施例 氫氣莫耳濃 轉化率 環己酮之 環己酮加環己醇之 度比（％) (%) 選擇率(％) 選擇率（％) 14 80 99.62 64.2 99.82 15 44 99.83 83.6 99.88 反應條件：每小時重量空間速度為2.3，氫對酚之莫耳比 為4，反應壓力為14.7 psig。 TF1004507 8 201235343 貫施例14與15之反應乃使用BASF-547970商用觸媒（含 〇.9%Pd)，當加入氫氣濃度比由8〇%降至44%時，反應產物 之環己酮選擇率由64.2%提升到83.6%，而反應整體之轉化 率及環己酮加環己醇的總量皆維持於99%及99.5%以上。 實施例 氫氣莫耳濃 轉化率 環己酮之 環己酮加環己醇之 度比（％) (%) 選擇率(°/。） 選擇率（％) 16 "* -------- __ ' 50 99.85 70.73 99.78 17 44 99.70 ----- --- 79.69 99.66 反應條件：每小時重量空間速度為2 5，氫對酚之莫耳比 為4 ’反應壓力為14.7 psig。 男把例16與17之反應乃使用BASF-547970商用觸媒（含 〇 9/<>I>d)，當加入氫氣濃度比由50°/。降至44%時，反應產物 ^衣己酮選擇率由70.7%提升到79.7%，而反應整體之轉化 率及％己綱加環己醇的總量皆維持於99%及99.5%以上。 一·間速度(WHSV)對反應結果之影響： 每小時重量 空間速度 貫施例 II彳環己酮之選環己酮加環己醇 18 19 20 21 1.3 1.5 1.8 2.5 (%) 99.84 99.98 99.91 95.84 擇率（％) 之選擇率（％) 93.94 95.12 96.38 96.59 99.90 99.91 99.91 99.95 TF1004507 9 201235343 反應條件：氫氣莫耳濃度比為58%，氫對酚之莫耳比為4, 反應壓力為14.7 psig。 實施例18至21之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當反應之每小時重量空間速度由 1.3逐步提升至2.5時，反應產物之環己酮選擇率由93.94% 提升到96.59%，而反應之環己酮加環己醇的總量維持於 99.9%以上。 三、壓力對反應結果之影響： 實施例 壓力 (psig) 轉化率 (%) 環己酮之選 擇率（％) 環己酮加環己醇之選 擇率（％) 22 11.3 99.43 96.83 99.97 23 13.2 99.49 96.16 99.97 24 15.2 99.82 95.38 99.94 25 17.2 99.52 95.10 99.96 26 19.2 99.62 94.38 99.96 反應條件：每小時重量空間速度為2.0，氫氣莫耳濃度比 為58%，氫對酚之莫耳比為4。 實施例22至26之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當反應之壓力由19.2 psig逐步 降低至11.3 psig時，反應產物之環己酮選擇率由94.38%提 升到96.83%，而反應整體之轉化率及環己酮加環己醇的總 TF1004507 10 201235343 量皆維持於99%及99.9%以上。 四、溫度對反應結果之影響： 實施例 溫度 CC) 轉化率 (%) 環己酮之選 擇率(％) 環己酮加環己醇之選 擇率(％) 27 157 94.69 96.36 99.98 28 161 97.18 96.19 99.97 29 164 99.64 95.13 99.98 30 169 99.32 94.37 99.95 反應條件：每小時重量空間速度為2.0，氫氣莫耳濃度比 為58%，氫對酚之莫耳比為4，反應壓力為14.7 psig。 實施例27至30之反應乃使用Johnson Matthey商用觸媒 (Type 355，含0.8% Pd)，當反應之溫度由157°C逐步提升 至169°C時，反應整體之轉化率由94.69%提升到99.32%， 而產物環己酮之選擇率則由96.36%降低至94.37%，而反應 之環己酮加環己醇的總量維持於99.9%以上。 五、觸媒鈀含量對反應結果之影響： 實施例 觸媒纪含量 轉化率 環己酮之 環己酮加環己醇之 (%) (%) 選擇率（％) 選擇率（％) 31 0.6 99.62 94.06 99.96 32 0.8 99.85 95.52 99.95 反應條件：每小時重量空間速度為2.0，氫氣莫耳濃度比 TF1004507 11 201235343 為58%，氫對酚之莫耳比為4，反應壓力為14.7 psig。 實施例31與32之反應乃使用Johnson Matthey商用觸 媒，在相同的每小時重量空間速度下，當觸媒鈀含量由0.6% 提高至0.8%時，反應整體之轉化率由99.62%提升到 99.85%，而產物環己酮之選擇率也由94.06%提升至 95.52%，而反應之環己酮加環己醇的總量維持於99.9%以More than through the cycloheximation reaction or g-hydrogenation reaction _ preparation; the reaction requires more stringent reaction conditions, and will be: a wide range of conversion via cyclohexane, by-products, resulting in the conversion of the reaction "^ Alcohol or organic acid = For the preparation of the industry, there is a method of producing energy and separating the complex self-lowering hydrogenation reaction to prepare cyclohexanone, which can be distinguished as a problem. As for the -step method of generating cyclohexanone by g and the two-step method of using the intermediate substance as the starting material. In contrast, (iv) direct production of hexanol to take the end of the cycle of the long-term S has the same one-step slanting $ industrial energy and cost loss has a distinct advantage in the production of a cyclohexanol dehydrogenation reaction A large amount of thermal energy = and a = reaction can be selected to be carried out in a liquid or gaseous state. In the process of preparing cyclohexanone by a step-by-step process, cyclohexanol and various J-products are produced. Thus, many purification steps and methods have been developed in this process. A multiple-distillation process and a purification step for preparing cyclohexanone by phenol hydrogenation are disclosed in, for example, WO 2009/131769 Al, WO 2009/080618 A1, and WO 2009/080620 A1. In addition, U. However, in the aforementioned patent documents, in order to overcome the disadvantage of poor selectivity of the reaction itself, it is necessary to add multiple times of distillation and purification of the bovine at the rear end of the reaction or to improve the selectivity of the product by improving the catalytic activity. In view of the above problems, the present invention proposes a method for producing a cyclohexyl-product by hydrogenation reaction which is high in efficiency, economical and can solve the problems inherent in commercial applications, and is diluted by gas in a process of gaseous hydrogenation to produce cyclohexanone. The concentration of hydrogen required for the reaction increases the selectivity of the ketone in the product while maintaining high conversion of the reaction. Furthermore, the method of the invention can also be applied to catalysts of different properties. SUMMARY OF THE INVENTION One object of the present invention is to provide a process for the preparation of cyclohexanone in which the disadvantages of one or more conventional processes can be overcome or at least reduced. The inventors of the present invention have found that in the process of producing a cyclohexene by phenol hydrogenation, the step of diluting the gas concentration by introducing additional gas can increase the productivity and reduce the energy consumption. According to a preferred embodiment of the present invention, a catalyst comprising at least one catalytically active first lanthanum metal is added to a reaction apparatus at a temperature of about 150 to 200 ° C and a pressure of 〇 22 22 The nitridation reaction is carried out under psig conditions, and the phenol is converted into cyclohexanone. The reaction apparatus comprises a feed tank, a preheating TF1004507 4 201235343 section, a vaporization section, a reactor, a condenser and a collection tank. In the initial stage of the reaction, the feed tank is heated to make the reactants melt, and is transported by a metering pump. The reactant phenol is pre-vaporized by preheating, and then enters the vaporization section together with the hydrogen and the diluent gas required for the reaction. Finally, the reactor is introduced into the reactor in the state of a mixed gas, and hydrogenation reaction is carried out with the catalyst filled therein, and the product formed by the reaction is sampled and collected after passing through the condenser. In the above process of the present invention, the total gas concentration of the hydrogen gas to the dilution gas molar Φ concentration ratio is between 0.1 and 15, preferably between 0.1 and 4; the catalyst comprises 0.5 to 1.0% of the Group 10 metal. And the Group 10 metal is selected from platinum or palladium, preferably palladium; the hydrogenation reaction is carried out under a condition that the ratio of hydrogen to phenol molar concentration is between 3 and 8; and the dilution is used The gas is preferably nitrogen. [Embodiment] The features and effects of the present invention are further illustrated by the following specific examples, but φ is not intended to limit the scope of the present invention. According to the preferred embodiment of the invention described above, the hydrogenation reaction is carried out under the reaction conditions of each of the examples to convert the phenol to cyclohexanone. I. Effect of hydrogen concentration on the reaction results: Example Hydrogen molar concentration conversion ratio of cyclohexanone to cyclohexanol (%) (%) Selectivity (%) Selectivity (%) 1 80 99.8 85.2 99.94 2 44 99.5 91.3 99.96 TF1004507 5 201235343 Reaction conditions: The hourly weight space velocity is 1.5, the hydrogen to phenol molar ratio is 4, and the reaction pressure is 14.7 psig. The reaction of Examples 1 and 2 was carried out using a Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the hydrogen concentration ratio was reduced from 80% to 44%, the selectivity of the reaction product cyclohexanone was increased by 85.2%. To 91.3%, the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 99.5% and above 99.9%. EXAMPLES Hydrogen molar concentration conversion ratio of cyclohexanone to cyclohexanol (%) (%) Selectivity (%) Selectivity (%) 3 80 99.8 88.1 99.90 4 44 99.3 91.8 99.97 Reaction conditions The hourly weight space velocity was 1.5, the hydrogen to phenol molar ratio was 4, and the reaction pressure was 7.3 psig. The reaction of Examples 3 and 4 was carried out using a Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the hydrogen concentration ratio was reduced from 80% to 44%, the cyclohexanone selectivity of the reaction product was increased by 88.1%. To 91.8%, the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 99.3% and above 99.9%. TF1004507 6 201235343 Example Hydrogen molar concentration conversion ratio of cyclohexanone to cyclohexanol (%) (%) Selectivity (%) Selectivity (%) 5 60 99.5 91.1 99.96 6 44 98.5 93.2 99.96 Reaction conditions: a weight space velocity of 2.3 per hour, a hydrogen to phenol molar ratio of 4, and a reaction pressure of 7.3 psig. The reaction of Examples 5 and 6 was carried out using a Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the hydrogen concentration ratio was reduced from 60% to 44%, the cyclohexanone selectivity of the reaction product was increased by 91.1%. To 93.2%, the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 98.5% and above 99.9%. EXAMPLES Hydrogen molar concentration ratio (%) Conversion rate (%) Selectivity of cyclohexanone (%) Selectivity of cyclohexanone plus cyclohexanol (%) 7 80 95.32 91.22 99.95 8 60 99.72 94.51 99.96 9 55 99.64 95.35 99.96 10 52 99.64 95.76 99.96 11 44 99.63 96.35 99.94 Reaction conditions: a weight space velocity of 2 per hour, a hydrogen to phenol molar ratio of 4, and a reaction pressure of 14.7 psig. The reactions of Examples 7 to 11 were carried out using Johnson Matthey commercial catalyst TF1004507 7 201235343 (Type 355, containing 0.8% Pd). When the hydrogen concentration ratio was reduced from 80% to 44%, the cyclohexanone selectivity of the reaction product was determined by 91.2% was increased to 96.4%, and the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 99% and 99.9% or more. EXAMPLES Hydrogen molar concentration ratio (%) Conversion rate (%) Selectance of cyclohexanone (%) Selectivity of cyclohexanone plus cyclohexanol (%) 12 80 99.8 44.2 99.85 13 44 99.5 66.8 99.79 Reaction conditions: The hourly weight space velocity was 1.5, the molar ratio of hydrazine to phenol was 4, and the reaction pressure was 14.7 psig. The reaction of Examples 12 and 13 was carried out using BASF-547970 commercial catalyst (containing 0.9% Pd). When the hydrogen concentration ratio was reduced from 80% to 44%, the cyclohexanone selectivity of the reaction product was increased from 44.2% to 66.8. %, and the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 99% and 99.5% or more. EXAMPLES Hydrogen molar concentration conversion ratio of cyclohexanone to cyclohexanol (%) (%) Selectivity (%) Selectivity (%) 14 80 99.62 64.2 99.82 15 44 99.83 83.6 99.88 Reaction conditions The hourly weight space velocity was 2.3, the hydrogen to phenol molar ratio was 4, and the reaction pressure was 14.7 psig. TF1004507 8 201235343 The reaction of Examples 14 and 15 was carried out using BASF-547970 commercial catalyst (containing 〇.9% Pd). When the concentration of hydrogen added was reduced from 8〇% to 44%, the cyclohexanone of the reaction product was selected. The rate increased from 64.2% to 83.6%, while the overall conversion rate of the reaction and the total amount of cyclohexanone plus cyclohexanol were maintained at 99% and above 99.5%. EXAMPLES Hydrogen molar concentration conversion ratio of cyclohexanone to cyclohexanol (%) (%) Selection rate (°/.) Selection rate (%) 16 "* ------ -- __ ' 50 99.85 70.73 99.78 17 44 99.70 ----- --- 79.69 99.66 Reaction conditions: hourly weight space velocity of 25, hydrogen to phenol molar ratio of 4 'reaction pressure of 14.7 psig. Males reacted with Examples 16 and 17 using BASF-547970 commercial catalyst (containing 〇 9/<>I>d) when the hydrogen concentration ratio was 50 °/. When the concentration was reduced to 44%, the selectivity of the reaction product was increased from 70.7% to 79.7%, and the overall conversion rate of the reaction and the total amount of the cyclohexanol were maintained at 99% and 99.5% or more. Effect of speed (WHSV) on the reaction results: hourly weight space velocity Example II: cyclohexanone selection cyclohexanone plus cyclohexanol 18 19 20 21 1.3 1.5 1.8 2.5 (%) 99.84 99.98 99.91 95.84 Selection rate (%) Selection rate (%) 93.94 95.12 96.38 96.59 99.90 99.91 99.91 99.95 TF1004507 9 201235343 Reaction conditions: hydrogen molar concentration ratio of 58%, hydrogen to phenol molar ratio of 4, reaction pressure of 14.7 psig. The reactions of Examples 18 to 21 were carried out using a Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the hourly weight space velocity of the reaction was gradually increased from 1.3 to 2.5, the cyclohexanone selectivity of the reaction product was 93.94. The % is increased to 96.59%, and the total amount of the reacted cyclohexanone plus cyclohexanol is maintained above 99.9%. Third, the effect of pressure on the reaction results: Example pressure (psig) conversion rate (%) cyclohexanone selectivity (%) cyclohexanone plus cyclohexanol selectivity (%) 22 11.3 99.43 96.83 99.97 23 13.2 99.49 96.16 99.97 24 15.2 99.82 95.38 99.94 25 17.2 99.52 95.10 99.96 26 19.2 99.62 94.38 99.96 Reaction conditions: an hourly weight space velocity of 2.0, a hydrogen molar concentration ratio of 58% and a hydrogen to phenol molar ratio of 4. The reactions of Examples 22 to 26 were carried out using a Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the pressure of the reaction was gradually reduced from 19.2 psig to 11.3 psig, the cyclohexanone selectivity of the reaction product was increased by 94.38%. To 96.83%, the total conversion of the reaction and the total TF1004507 10 201235343 of cyclohexanone plus cyclohexanol were maintained at 99% and 99.9% or more. 4. Effect of temperature on the reaction results: Example temperature CC) Conversion rate (%) Selectivity of cyclohexanone (%) Selectivity of cyclohexanone plus cyclohexanol (%) 27 157 94.69 96.36 99.98 28 161 97.18 96.19 99.97 29 164 99.64 95.13 99.98 30 169 99.32 94.37 99.95 Reaction conditions: an hourly weight space velocity of 2.0, a hydrogen molar concentration ratio of 58%, a hydrogen to phenol molar ratio of 4, and a reaction pressure of 14.7 psig. The reactions of Examples 27 to 30 were carried out using Johnson Matthey commercial catalyst (Type 355, containing 0.8% Pd). When the temperature of the reaction was gradually increased from 157 ° C to 169 ° C, the overall conversion of the reaction was increased from 94.69% to 99.32%, while the selectivity of the product cyclohexanone decreased from 96.36% to 94.37%, while the total amount of cyclohexanone plus cyclohexanol in the reaction was maintained above 99.9%. V. Effect of catalyst palladium content on the reaction results: Example Catalyst content conversion rate Cyclohexanone cyclohexanone plus cyclohexanol (%) (%) Selectivity (%) Selectivity (%) 31 0.6 99.62 94.06 99.96 32 0.8 99.85 95.52 99.95 Reaction conditions: The hourly weight space velocity is 2.0, the hydrogen molar concentration is 58% compared to TF1004507 11 201235343, the hydrogen to phenol molar ratio is 4, and the reaction pressure is 14.7 psig. The reactions of Examples 31 and 32 were carried out using Johnson Matthey commercial catalyst. At the same hourly weight space velocity, when the catalytic palladium content was increased from 0.6% to 0.8%, the overall conversion of the reaction was increased from 99.62% to 99.85. %, and the selectivity of the product cyclohexanone was also increased from 94.06% to 95.52%, while the total amount of cyclohexanone plus cyclohexanol in the reaction was maintained at 99.9%.
TF1004507 12TF1004507 12