Development of the Sulfide-Based Catalysts for the CO Hydrogenation Reaction in the Presence of H_2S

H_2S存在下CO加氢反应硫化物基催化剂的研制

• 批准号: 10450298
• 负责人: YAMADA Muneyoshi
• 金额: $ 7.04万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450298/
• 关键词: Synthesis gas; Higher alcohol synthesis; Mo sulfide; Sulfur tolerance; Coordinative unsaturation; FTIR spectroscopy; EXAFS spectroscopy; High surface area; アルコール合成; 耐硫黄被毒性; モリブデン系硫化物触媒; 高活性化; 銅; 亜鉛系触媒; 混合アルコール合成; 耐硫黄性触媒; アルコール生成サイト; 高圧キャラ; Synthesis gas; Higher alcohol synthesis; Mo sulfide; Sulfur tolerance; Coordinative unsaturation; FTIR spectroscopy; EXAFS spectroscopy; High surface area; アルコール合成; 耐硫黄被毒性; モリブデン系硫化物触媒; 高活性化; 銅; 亜鉛系触媒; 混合アルコール合成; 耐硫黄性触媒; アルコール生成サイト; 高圧キャラ

Synthesis of higher alcohol from CO+H_2 (syngas) on alkali metal-promoted MoS_2 catalysts has been studied because of their advantages of a sulfur tolerance. However, the activity for the synthesis of the higher alcohol of these catalysts is lower than those of the Cu/Zn based catalysts. Besides, the chain growth probability of the formed alcohol lies in the range from 0.2 to 0.25, which indicates that the alcohol is mainly composed of methanol. The present work tried to make clear factors in determining the activity and selectivity for the CO hydrogenation reaction of the alkali metal-promoted MoS_2 catalysts. Based on the results, we developed a novel preparation method for the catalysts which show the higher activity and selectivity for the synthesis of the higher alcohol.MoS_2-based catalysts are widely used for the hydrotreating reaction of the oil fractions. It is suggested that sulfur-vacant sites are formed on the sulfides under the reducing conditions and are involved in the r … More eaction. In the case of the CO hydrogenation reaction on the MoS_2-based catalysts, however, the role of the sulfur vacant sites has not been made clear yet. The present work found that the selectivity for C_2-C_3 alcohol of K-MoS_2/Al_2O_3 increased with increasing the time on-stream, which accompanies the desorption of H_2S.In-situ FTIR spectroscopy coupled with the adsorption of NO probe molecule showed that the surface fine structure of the catalyst changed by the desorption of H_2S.By combining the results obtained by FTIR spectroscopy with those by EXAFS spectroscopy, it was suggested that the coordinatively unsaturated K sites and the coordinatively unsaturated Mo sites interacted with K species were formed under the reaction conditions. It was also suggested that the surface fine structure of the catalyst changed dynamically depending on the concentration of the gas-phase H_2S.To increase the number of the interaction species between K and Mo species as was suggested by FTIR and EXAFS spectroscopy, the present work tried to spread the alkali metal species uniformly over the surface of MoS_2 having the high surface area. The developed catalyst showed the higher activity for the synthesis of C_2-C_4 alcohol with the higher chain growth probability than the conventional (low surface area) catalyst. Less

由于它们具有硫耐受性的优势，因此研究了碱金属促进的MOS_2催化剂中CO+H_2（Syngas）较高的酒精的合成。但是，这些催化剂的较高酒精合成的活性低于基于Cu/Zn的催化剂的活性。此外，形成的酒精的链生长概率在0.2至0.25范围内，这表明酒精主要由甲醇组成。目前的工作试图在确定碱金属促进的MOS_2催化剂的CO氢化反应的活性和选择性方面做出明确的因素。基于结果，我们开发了一种新型的制备方法，用于催化剂，该方法显示出较高的活性和选择性较高的酒精。基于MOS_2的催化剂被广泛用于油分数的水力发电反应。建议在还原条件下在硫化物上形成硫酸位点，并参与R…更多的发作。但是，对于基于MOS_2的催化剂的CO氢化反应，尚未明确表明硫空位位点的作用。目前的工作发现，C_2-C_3 K-MOS_2/AL_2O_3酒精的选择性随着时间的增加而增加，这涉及脱附H_2s.in-Situ ftir光谱副本，与NO探针分子的添加添加的添加性相连，与催化剂的表面上的结构相结合了H_2的表面上的结构。通过EXAFS光谱法，在反应条件下形成了协调不饱和的K位点和与K物种相互作用的协调不饱和的MO位点。还提出，催化剂的表面细胞结构取决于气相H_2s的浓度，以增加K和MO种之间的相互作用物种的数量，如FTIR和EXAFS光谱所建议的那样，目前的工作试图在MOS_2的表面上均匀地散布碱金属物种。与常规（低表面积）催化剂相比，开发的催化剂显示出具有更高链生长概率的C_2-C_4醇的活性。较少的