Development of a next generation cracking catalyst based on analysis of acidic property and structure of active site on USY zeolite

基于USY沸石酸性和活性位点结构的新一代裂化催化剂的开发

• 批准号: 17560681
• 负责人: KATADA Naonobu
• 金额: $ 1.95万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17560681/
• 关键词: zeolite; alkane cracking; petroleum refinery; solid acid catalyst; ammonia IRMS-TPD; ultrastable Y zeolite; alkylation of aromatics; EDTA

Properties of Bronsted and Lewis acid sites and number of Bronsted acid strength of OH groups on various zeolites became able to be measured by developing the ammonia IRMS-TPD method. Treatment of USY zeolite with an EDTA-salt with neutral property increased strong Bronsted aridity. The presence of strained tetra-coordinated and extraframework Al species on EDTA-USY, this is considered to be the origin of the strong Bronsted acidity. This was identified by 16T NMR. By the IRMS-TPD, the string acidity of OH was directly observed, and this was the first direct observation of active site for alkane cracking on USY.Applying with quantum calculation, it was clarified that extraframework AlOH coordinated at the window of hexagonal prism enhanced the Bronsted acidity of adjacent OH. This is the origin of cracking activity of USY. At the same position, Ca etc. also enhanced the acidity.Thus the structure of alkane cracking site was clarified. Application of these catalysts to octane cracking showed a potential activity for next generation catalyst.In addition, acidic property of a mesoporous zeolite, which was expected to have a potential for cracking of heavy oil, has been analyzed for the first time. WO_3/ZrO_2 was also analyzed. A method for analysis of the adsorption heat of aromatic molecule on zeolite was developed.

用氨IRMS-TPD法测定了各种沸石分子筛上的质子酸和刘易斯酸中心的性质以及OH基的质子酸强度。用中性EDTA盐处理USY分子筛，可增强分子筛的布朗斯台德干燥度。在EDTA-USY上存在应变的四配位和骨架外Al物种，这被认为是强布朗斯台德酸性的起源。这通过16 T NMR鉴定。通过IRMS-TPD直接观察到了OH的弦酸性，这是首次直接观察到USY上烷烃裂解的活性中心，并通过量子计算证实了骨架外AlOH配位在六棱柱窗口处增强了相邻OH的Bronsted酸性。这是超稳Y丝裂解活性的根源。在同一位置上，Ca等也增强了酸性，从而明确了烷烃裂解中心的结构。这些催化剂在辛烷裂解中的应用显示出了下一代催化剂的潜在活性。此外，首次分析了有望用于重油裂解的介孔分子筛的酸性。对WO_3/ZrO_2进行了分析。本文提出了一种分析芳烃分子在沸石上吸附热的方法。

项目成果

Thermal Transformation Process of a Keggin-Type Mixed Heteropoly Acid, H4PNbW 11O40, the Precursor of the H3PO4-WO3-Nb2O5 Catalyst

Keggin 型混合杂多酸 H4PNbW 11O40（H3PO4-WO3-Nb2O5 催化剂前体）的热转化过程

• 发表时间: 2007
• 期刊: J. Catal 245
• 作者: K. Okumura;K. Yamashita;K. Yamada;M. Niwa
• 通讯作者: M. Niwa

Identification and Measurements of Strong Breasted Acid Site in Ultra-Stable Y (USY) Zeolite

超稳定 Y (USY) 沸石中强排酸位点的识别和测量

• 发表时间: 2006
• 期刊: J. Phys. Chem., B 110
• 作者: M. Niwa;K. Suzuki;K. Isamoto;N. Katada
• 通讯作者: N. Katada

A Theoretical Study on Breasted Acidity of WO3 Clusters Supported on Metal Oxide Supports by "Paired Interacting Orbitals" (PIO) Analysis

通过“成对相互作用轨道”（PIO）分析对金属氧化物载体上WO3团簇的胸状酸度进行理论研究

• 发表时间: 2006
• 期刊: Catal. Today 111
• 作者: A. Shiga;N. Katada;M. Niwa
• 通讯作者: M. Niwa

チタニア担持酸化タングステンモノレイヤー固体酸触媒によるエチレン水和

二氧化钛负载氧化钨单层固体酸催化剂乙烯水合

• 发表时间: 2007
• 作者: 片田直伸;井関洋平;志知 明;尾崎和洋;藤本憲一;椿 卓也;丹羽 幹;藤田伸夫;石野 巌
• 通讯作者: 石野 巌

Hydration of Ethylene on Tungsta Monolayer Catalyst Loaded on Titania

二氧化钛负载钨单层催化剂上乙烯的水合

• 发表时间: 2007
• 作者: Naonobu;Katada;et. al.
• 通讯作者: et. al.