权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

A Study on the Characterization of Hydrodesulfurization Catalysts by Magnetic Properties of Co toward the Development of Highly Active Catalysts

Co磁性表征加氢脱硫催化剂的研究及高活性催化剂的开发

基本信息

批准号：
16360404
负责人：
OKAMOTO Yasuaki
金额：
$ 8.64万
依托单位：
Shimane University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

The salient findings in this research project are as follows:1. The Co sulfide species in the Co-Mo-S phase show an antiferromagnetic behavior. The magnetic susceptibility of the Co atoms was simulated by a theoretical equation assuming the formation of Co dimmer clusters with Co-S-Co bonding, in conformity with the NO adsorption, which shows the maximum NO adsorption capacity is NO/Co = 1/1 molar ratio. The proposed Co-Mo-S structure was supported by our recent XAFS analysis of CVD-Co/MoS_2 catalysts.2. The addition of boron to Co-Mo/Al_2O_3 was studied to improve the hydrodesulfurization activity. It was found that the addition of boron increases the TOF by 1.6 times, indicating the ace reactions, accordingly resulting in weaker interactions between Mo oxides and Al_2O_3 surface. The dispersion of MoS_2 was decreased by the addition of boron because of ence in the dispersion of MoS2 particles.3. The intrinsic activity of the Co-Mo-S structure was increased by sulfiding at a high temperatur-Mo-S structure showed a much less activity because of strong Mo-O-Al bonding. However, the addition of boron decreased the sulfidation temperature for the formation of Type II. The thermal stability of the Co-Mo-S phase was decreased by the addition of boron.4. Highly dispersed Co sulfide clusters were successfully prepared in zeolite pores using Co(CO)_3NO as a precursor. The structure depended on the type of the host zeolite. It was found that Co sulfide clusters react with zeolite protons to form Co2+ cations liberating H_2S. The hydrodesulfurization activity of the Co_sulfide clusters depended on the structure and residual OH groups.5. It is proposed that highly active hydrotreating catalysts are prepared by synthesizing highly dispersed Co-Mo-S Type II by modifying the interactions between MoS_2 particles and support surface. Simultaneous use of boron and chelating agents will be very effective for the developments of highly active ultra-deep hydrodesulfurization catalysts.

本研究的主要发现如下：1.Co-Mo-S相中的Co硫化物物种表现出反铁磁行为。用假设Co-S-Co成键形成Co二聚体团簇的理论方程模拟了Co原子的磁化率，与NO的吸附一致，表明NO的最大吸附容量为NO/Co=1/1摩尔比。我们最近对CVD-Co/MoS_2催化剂的XAFS分析支持了所提出的Co-Mo-S结构。研究了在Co-Mo/Al_2O_3催化剂中添加硼以提高加氢脱硫活性的方法。结果表明，B的加入使催化剂的TOF增加了1.6倍，说明表面发生了ACES反应，导致了Mo氧化物与Al_2O_3表面的相互作用减弱。在MoS_2颗粒的分散过程中，由于硼的存在，降低了MoS_2的分散度。高温硫化提高了Co-Mo-S结构的本征活性--由于Mo-O-Al键较强，Mo-S结构的本征活性较低。但B的加入降低了第二类相形成的硫化温度，降低了Co-Mo-S相的热稳定性。以Co(CO)3NO为前驱体，在分子筛孔内成功制备了高分散的硫化钴团簇。其结构取决于主体沸石的类型。研究发现，硫化钴团簇与沸石质子反应生成释放H_2S的Co2+阳离子。钴硫化物簇合物的加氢脱硫活性与其结构和残留的羟基有关。提出了通过修饰MoS_2颗粒与载体表面的相互作用，合成高分散的Co-Mo-S II型加氢精制催化剂。同时使用硼和络合剂将是开发高活性超深度加氢脱硫催化剂的有效手段。

项目成果

期刊论文数量（38）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Effect of Boron Addition on the Intrinsic Activity of Al_2O_3-supported Co-W and Co-Mo Sulfide Catalysts for the Hydrodesulfurization of Thiophene

添加硼对Al_2O_3负载Co-W和Co-Mo硫化物催化剂噻吩加氢脱硫本征活性的影响

DOI：
发表时间：
2006
期刊：
Bull. Chem. Soc. Jpn. 79
影响因子：
0
作者：
Usman;Takeshi Kubota;Ichiro Hiromitsu;Yasuaki Okamoto;Usman;Usman
通讯作者：
Usman

Thermal Stability of the Co-Mo-S Sturucture as Studied bu a CVD Technique using Co(CO)_3NO

使用 Co(CO)_3NO 的 CVD 技术研究 Co-Mo-S 结构的热稳定性

DOI：
发表时间：
2006
期刊：
Ind. Eng. Chem. Res. 45
影响因子：
0
作者：
Usman;Takeshi Kubota;Ichiro Hiromitsu;Yasuaki Okamoto;Usman;Usman;Usman
通讯作者：
Usman

The Structure of the Active Sites of Co-Mo Hydrodesulfurization Catalysts as Studied by Magnetic Susceptibility Measurement and NO Adsorption

磁化率测量和NO吸附研究Co-Mo加氢脱硫催化剂活性位点结构

DOI：
发表时间：
2005
期刊：
J. Phys. Chem. B 109
影响因子：
0
作者：
Takeshi Kadono;Takeshi Kubota;Ichiro Hiromitsu;Yasuaki Okamoto;Usman;Usman;Takeshi Kadono;Yasuaki Okamoto
通讯作者：
Yasuaki Okamoto

Effect of Boron Addition on a MoO_3/Al_2O_3 Catalyst : Physicochemical Characterisation

添加硼对 MoO_3/Al_2O_3 催化剂的影响：物理化学表征

DOI：
发表时间：
2005
期刊：
Appl. Catal. A, General 286
影响因子：
0
作者：
Takeshi Kadono;Takeshi Kubota;Ichiro Hiromitsu;Yasuaki Okamoto;Usman;Usman;Takeshi Kadono;Yasuaki Okamoto;Takeshi Kubota;Usman
通讯作者：
Usman

Characterization of highly dispersed cobalt sulfide catalysts by X-ray absorption fine structure and magnetic properties