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.

通过开发氨 IRMS-TPD 方法，可以测量各种沸石上 OH 基团的布朗斯台德和路易斯酸位点的性质以及布朗斯台德酸强度的数量。用具有中性特性的 EDTA 盐处理 USY 沸石增加了强烈的布朗斯台德干燥度。 EDTA-USY 上存在应变四配位和骨架外 Al 物种，这被认为是强布朗斯台德酸度的起源。这是通过 16T NMR 鉴定的。通过IRMS-TPD，直接观察到了OH的串酸性，这是USY上首次直接观察到烷烃裂解活性位点。应用量子计算，阐明了在六棱柱窗口配位的骨架外AlOH增强了烷烃裂解活性。相邻 OH 的布朗斯台德酸度。这就是USY裂解活性的起源。在同一位置，Ca等也增强了酸性，从而阐明了烷烃裂解位点的结构。这些催化剂在辛烷裂化中的应用显示出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化的介孔沸石的酸性性质。还分析了WO_3/ZrO_2。建立了芳香族分子在沸石上吸附热的分析方法。

项目成果

Cooperative effect induced by the mixing of Na-ZSM-5 and Pd/H3PW12O40/SiO2 in the selective catalytic reduction of NO with aromatic hydrocarbons

• DOI: 10.1016/j.apcatb.2007.04.008
• 发表时间: 2007-09
• 期刊: Applied Catalysis B-environmental
• 影响因子: 22.1
• 作者: R. Yoshimoto;T. Ninomiya;K. Okumura;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

Changes in Acidic and Catalytic Properties by Cation Exchange of Y Zeolite with Alkaline Earths

Y型沸石与碱土的阳离子交换导致酸性和催化性能的变化

• 发表时间: 2007
• 作者: Takayuki;Noda;et. al.
• 通讯作者: et. al.

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