Selective Hydrogenation Processes by Means of a Catalyst Preparation Method Using Volatile Metal Complexes

利用挥发性金属配合物的催化剂制备方法的选择性加氢过程

• 批准号: 05650777
• 负责人: MIURA Hiroshi
• 金额: $ 1.34万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650777/
• 关键词: Volatile Complex; Bimetallic Catalyst; Selective Hydrogenation; Crotonaldehyde; Crotylalcohol; Zirconium dipivaloilmethanato

Preparation of Co-based bimetallic catalysts has been tried using volatile metal complexes as precursors, and a highly selective catalyst in partial hydrogenation of crotonaldehyde has been found. Addition of Zr (dpm) 2 complex in Co/A1203 improved both activity and selectivity of the catalyst in hydrogenation of crotonaldehyde to form crotylalcohol. Other Zr-complexes, less volatile than Zr (dpm) 2, suggested inferior effect, and the volatility of the precursor is the critical factor. The state of Zr after decomposition of Zr (dpm) 2 was studied. The precursor decomposed in hydrogen flow in the presence of Co and deposited a thin film consisting of ZrO2 as the main component. However low valent Zr (Zr^0) was also found by XPS,and such low valent Zr seemed to result in the high selectivity. Formation of such low valent Zr was unique for our preparation method. The optimization of the reaction condition was tired and finally highest yield of crotylalcohol was found to be more than 80%. This catalyst is more active than any other catalyst reported in the literature. Addition of Zr in Co accelerated the C=O hydrogenation, and suppressed the C=C hydrogenation.Our new method of catalyst preparation was effective in introducing catalyst promoter in special valence state, and useful in the development of new catalyst systems.

以挥发性金属配合物为前驱体制备了钴基双金属催化剂，发现了一种具有高选择性的巴豆醛部分加氢催化剂。在Co/A1203中加入Zr (dpm) 2配合物，提高了巴豆醛加氢制巴豆醇催化剂的活性和选择性。其他Zr-配合物的挥发性不如Zr (dpm) 2，表明其效果较差，前驱体的挥发性是关键因素。研究了Zr (dpm) 2分解后Zr的状态。前驱体在Co存在下在氢气流中分解，形成以ZrO2为主要成分的薄膜。然而，XPS也发现了低价Zr (Zr^0)，这种低价Zr似乎导致了高选择性。这种低价Zr的形成在我们的制备方法中是独一无二的。通过对反应条件的优化，确定了丁醇的最高产率可达80%以上。这种催化剂比文献中报道的任何其他催化剂都更活跃。Co中Zr的加入加速了C=O氢化反应，抑制了C=C氢化反应。该方法有效地引入了特殊价态的催化剂促进剂，对新型催化剂体系的开发具有重要意义。

项目成果

佐藤英樹、三浦弘: "イソブタン脱水素反応における担持白金触媒の酸化亜鉛の添加効果" 石油学会誌. 38. 34-39 (1995)

Hideki Sato、Hiroshi Miura：“在异丁烷脱氢反应中向负载型铂催化剂中添加氧化锌的效果”日本石油学会杂志 38. 34-39 (1995)。

H.Miura 他: "Preparation of Egg Shell type Pd-Ag Bimetallic Catalysts by Selective Deposition" Proc.10th Intern.Congr.Catal.2379-2382 (1993)

H. Miura 等人：“通过选择性沉积制备蛋壳型 Pd-Ag 双金属催化剂”Proc.10th Intern.Congr.Catal.2379-2382 (1993)

三浦弘、市岡和之、斉藤昌男、松田常雄: "アルミナ担持バイメタリック触媒を用いたクロトンアルデヒド選択水素化反応によるクロチルアルコールの合成" 日本化学会誌. 1994. 487-489 (1994)

Hiroshi Miura、Kazuyuki Ichioka、Masao Saito、Tsuneo Matsuda：“使用氧化铝负载的双金属催化剂选择性氢化巴豆醛合成巴豆醇”日本化学学会杂志 1994 年。487-489 (1994)。

Hiroshi Miura, Kazuyuki Ichioka, Masao Saito, Tsuneo Matsuda: "Synthesis of crotylalcohol by selective hydrogenation of crotonaldehyde over alumina supported bimetallic catalysts" Nippon Kagaku Kaishi. 487-489 (1994)

Hiroshi Miura、Kazuyuki Ichioka、Masao Saito、Tsuneo Matsuda：“在氧化铝负载的双金属催化剂上选择性氢化巴豆醛合成巴豆醇”Nippon Kagaku Kaishi。

Richard D.Gonzalez, Hiroshi Miura: "Preparation of SiO2-and A12O3-supported clusters of Pt group metals" Catal.Rev.-Sci.Eng. 36. 145-177 (1994)

Richard D.Gonzalez、Hiroshi Miura：“SiO2 和 A12O3 负载的 Pt 族金属簇的制备”Catal.Rev.-Sci.Eng。