FTIR Study of Adsorbed Nitrogen and hydrogen on Ruthenium Catalyst for Next Generation Ammonia Synthesis

用于下一代氨合成的钌催化剂上吸附氮和氢的 FTIR 研究

• 批准号: 07455436
• 负责人: AIKA Kenichi
• 金额: $ 0.64万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07455436/
• 关键词: Ammonia Synthesis; Nitrogen Activation; FTIR of adsorbed N_2; FTIR of adsorbed H; Ruthenium Catalyst; Metal Cluster; Support Effect; Promoter Effect; ルテニウムクラスター

Iron catalysts suffer from ammonia poisoning, because of which one-pass conversion is controlled to keep the low value. Ruthenium was started to be used as a second generation ammonia catalyst because it has an advantage not to be poisoned by ammonia, however it has a disadvantage of hydrogen poisoning. The active ruthenium catalyst developed under 1 atom test some times are not active under the industrial high pressure condition because of the strong hydrogen poisoning. The purpose of this work is to develop a Ru-catalyst which does not adsorb hydrogen strongly and to check the adsorption behavior of hydrogen and nitrogen by FTIR technique.1) Various Ru catalysts were synthesized from Ru_3 (CO)_<12>, various supports (MgO,CeO_2, A.C., Al_2O_3, etc.), and various promoters (CsOH,BaO,etc.). Ru cluster composed by six Ru atoms including one N atom at the center was also synthesized and supported on MgO.2) The structure of Ru Cluster was analyzed by EXAFS,XPS,XRD,TEM,etc.The size of cluster and average co-ordination number was calculated.3) Two types of adsorbed hydrogen (on-top and bridge) atom were observed by FTIR.Two types were observed on Ru/MgO,but on Ru/CeO_2 mainly on-top hydrogen was observed.4) Ammonia synthesis and kinetics were studied. Hydrogen poisoning was strong in Ru/MgO but weak on Ru/CeO_2. Ru/CeO_2 was found to become highly active when it was treated by hydrogen at 873K.

铁催化剂容易发生氨中毒，一次转化率受到控制，以保持较低的转化率。由于Ru具有不被氨中毒的优点，因此开始作为第二代氨催化剂使用，但它也有氢中毒的缺点。在1原子试验条件下研制的活性Ru催化剂，由于强氢中毒，在工业高压条件下有时会失活。1)以Ru_3(CO)_2、不同载体(MgO、CeO_2、Ac、Al_2O_3等)和不同助剂(CsOH、BaO等)为原料，合成了多种Ru催化剂。合成了六个Ru原子组成的Ru团簇，其中一个是中心N原子。2)用EXAFS、XPS、X射线衍射仪、透射电子显微镜等分析了Ru团簇的结构，计算了团簇的大小和平均配位数。3)FTIR观察到两种类型的吸附氢原子(顶部和桥式)。在Ru/MgO上观察到两种类型的吸附氢原子，而在Ru/CeO_2上观察到以顶部氢原子为主的两种类型。4)氨合成和动力学研究。Ru/MgO催化剂有较强的氢中毒现象，而Ru/CeO_2催化剂的氢中毒较弱。

项目成果

Hiroshi KURAKATA,Yasuo IZUMI and Ken-ichi AIKA: "Ethanol Synthesis from Carbon Dioxide on TiO_2-supported[Rh_<10>Se]Catalyst" J.Chem.Soc.,Chem.Commun.389-390 (1996)

Hiroshi KURAKATA、Yasuo IZUMI 和 Ken-ichi AIKA：“TiO_2 负载的[Rh_<10>Se]催化剂上二氧化碳合成乙醇”J.Chem.Soc.，Chem.Commun.389-390 (1996)

Hiroshi KURAKATA Yasuo IZUMI and Ken-ichi AIKA: "Ethanol Synthesis from Carbon Dioxide on TiO_2 -supported [Rh_<10>Se] Catalyst" J. Chem. Soc., Chem. Commun.(in press.). (1996)

Hiroshi KURAKATA Yasuo IZUMI和Ken-ichi AIKA：“在TiO_2负载的[Rh_ 10 Se]催化剂上从二氧化碳合成乙醇” J. Chem。

Ken-ichi AIKA and T.Karasuda: "Study on the Active Site Structure of MgO Catalysts for Oxidative Coupling of Methane;Catalysts in Petroleum Refining & Petrochemical Industries 1995" M.Absi-Halabi et al.(eds.)Elsevier Science B.V., 598 (1996)

Ken-ichi AIKA 和 T.Karasuda：“甲烷氧化偶联 MgO 催化剂的活性位点结构研究；石油精炼催化剂

秋鹿研一: "地球環境浄化に関連する触媒プロセス;地球環境問題に挑戦する(黒田、宝田共編、化学工学会)" 培風館, 119-129 (1996)

Kenichi Akishika：“与全球环境净化相关的催化过程；挑战全球环境问题（化学工程师学会黑田和宝田共同编辑）” Baifukan，119-129（1996）

K.AIKA,and T.KARASUDA: Study on the Active Site Structure of MgO Catalysis for Oxidative Coupling of Methane, Catalysts in Petroleum Refining & Petrochemical Industries 1995, M.Absi-Halabi et al. (eds.). Elsevier B.V., 397 (1996)

K.AIKA和T.KARASUDA：石油精炼催化剂甲烷氧化偶联MgO催化活性位点结构研究