Development of useful metal catalysts for hydrotreatment of diesel fuel to decrease particulate matters in diesel exhaust.

开发用于柴油加氢处理的有用金属催化剂，以减少柴油废气中的颗粒物。

• 批准号: 13650837
• 负责人: MIURA Hiroshi
• 金额: $ 2.18万
• 依托单位: Saitama university
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650837/
• 关键词: polyaromatic hydrocarbons; naphthalene hydrogenation; supported Pd catalysts; bimetallic catalysts; dimethyldisulfide; metal-sulfur bond strength; mixed oxide; sulfur tolerance; ディーゼル黒煙; 多環芳香族; 水素化精製触媒; Pd触媒; Pd-Ptバイメタリック触媒; Al_2O_3-TiO_2; 複

To develop useful metal catalysts for hydrogenation of aromatic hydrocarbons in diesel fuel, we have studied naphthalene hydrogenation over supported Pd catalysts in the presence of dimethyldisulfide as a sulfur compound.(1)Naphthalene hydrogenation over Pd/Al_2O_3, Pd/SiO_2, Pd/TiO_2, Pd/TiO_2-SiO_2, and Pd/TiO_2-Al_2O_3 cal alysts was studied in the presence or absence of dimethyldisulfide (DMDS). As a results, the order of TOP (turn over frequency) was Pd/TiO_2-Al_2O_3 > Pd/TiO_2-SiO_2 > Pd/TiO_2 > Pd/Al_2O_3 > Pd/SiO_2(2)Pd-Pt/TiO_2 and Pd-Pt/TiO_2 catalysts were prepared by a co-impregnation method and evaluated in the hydrogenation of naphthalene in the presence of dimethyldisulfide. All Pd-Pt/TiO_2 bime tallic catalysts showed the higher TOF than the Pt/TiO_2 catalyst. Pd-Pt/TiO_2 containing 50mol% Pd showed the highest TOF in the catalysts tested. Meanwhile The highest TOF of Pd-Pt/Al_2O_3 were obtained at the content of 80mol% Pd. The TOF of Pd-Pt/Al_2O_3 containing 80mol% Pd was 8 times and 18 times higher than those of Pd/Al_2O_3 and Pt/Al_2O_3, respectively.(3)As compared with Pd/Al_2O_3,Pd/TiO_2 showed high TOF and sulfur tolerance, in both the presence of DMDS and the absence of DMDS. Pd-S bond strength was determined by temperature-programmed reduction (H_2S-TPR) profiles. The results show that desorption of H_2S from sulfided Pd/TiO_2 occurs at 553 K, whereas desorption of H_2S from sulfided Pd/Al_2O_3 requires a higher temperature (773 K), indicating that the Pd-S bond in Pd/TiO_2 is significantly weaker than that in Pd/Al_2O_3. Consequently, in Pd/TiO_2 clean surfaces of Pd metals are highly exposed as active sites for the naphthalene hydrogenation in the presence of dimethyldisulfide.

为了开发适用于柴油燃料中芳烃加氢的金属催化剂，我们研究了在二甲基二硫醚作为硫化合物存在下，负载型Pd催化剂上萘的加氢反应。(1)Pd/Al_2O_3、Pd/SiO_2、Pd/TiO_2、Pd/TiO_2-SiO_2上的萘加氢反应，以及 在存在或不存在二甲基二硫醚(DMDS)的情况下研究了Pd/TiO_2-Al_2O_3催化剂。结果表明,TOP(翻转频率)顺序为Pd/TiO_2-Al_2O_3>Pd/TiO_2-SiO_2>Pd/TiO_2>Pd/Al_2O_3>Pd/SiO_2(2)采用共浸渍法制备了Pd-Pt/TiO_2和Pd-Pt/TiO_2催化剂,并在萘加氢反应中进行了评价。 二甲基二硫醚的存在。所有Pd-Pt/TiO_2双金属催化剂均表现出比Pt/TiO_2催化剂更高的TOF。含50mol%Pd的Pd-Pt/TiO_2在测试的催化剂中表现出最高的TOF。同时Pd含量为80mol%时Pd-Pt/Al_2O_3的TOF最高。含80mol%Pd的Pd-Pt/Al_2O_3的TOF分别是Pd/Al_2O_3和Pt/Al_2O_3的8倍和18倍。(3)与Pd/Al_2O_3相比,Pd/TiO_2在DMDS存在和不存在的情况下均表现出较高的TOF和硫耐受性。 Pd-S 结合强度通过程序升温还原 (H_2S-TPR) 曲线测定。结果表明，硫化Pd/TiO_2中H_2S的解吸发生在553 K，而硫化Pd/Al_2O_3中H_2S的解吸需​​要更高的温度(773 K)，这表明Pd/TiO_2中的Pd-S键明显弱于Pd/Al_2O_3中的Pd-S键。因此，在 Pd/TiO_2 中，Pd 金属的清洁表面高度暴露，作为二甲基二硫醚存在下萘氢化的活性位点。

项目成果

K.Ito, H.Kurokawa, M.Ohshima, K.Sugiyama, H.Miura: "Hydrogenation of naphthalene in the presence of dimethyldisulfide over titania-and alumina-supported Pd-Pt bimetallic catalysts"Fourth Tokyo Conference on Advanced catalytic Science and Technology. 374 (

K.Ito、H.Kurokawa、M.Ohshima、K.Sugiyama、H.Miura：“在二甲基二硫醚存在下，二氧化钛和氧化铝负载的 Pd-Pt 双金属催化剂上萘的氢化”第四届东京先进催化科学会议

K. Ito, H. Kurokawa, M. Ohshima, K. Sugiyama, H. Miura: "Hydrogenati on of naphthalene in the presence of dimethyldisulfide over titania- and alumina-supported Pd-Pt bimetallic catalysts"Fourth Tokyo Conference on Advanced catalytic Science and Technology

K. Ito、H. Kurokawa、M. Ohshima、K. Sugiyama、H. Miura：“在二甲基二硫存在下，二氧化钛和氧化铝负载的 Pd-Pt 双金属催化剂上萘的氢化”第四届东京先进催化科学会议

K. Ito, J. - Tamura, M. Ohshima, H. Kurokawa, K. Sugiyama, H. Miura: "Hydrogenation of naphthalene over Pd/TiO_2-SiO_2 catalysts"J. of the Japan Petroleum Institute. 46, (1). 84-85 (2003)

K. Ito, J. - Tamura, M. Ohshima, H. Kurokawa, K. Sugiyama, H. Miura：“Pd/TiO_2-SiO_2 催化剂上萘的氢化”J。

K. Ito, T. Tomino, M. Ohshima, H. Kurokawa, K. Sugiyama, H. Miura: "Sulfur Tolerance of Pd/Al_2O_3 and Pd/TiO_2 in Naphthalene Hydrogenation in the Presence of Dimethyldisulfide"Applied Catalysis A : General. in press.

K. Ito、T. Tomino、M. Ohshima、H. Kurokawa、K. Sugiyama、H. Miura：“二甲基二硫醚存在下萘氢化中 Pd/Al_2O_3 和 Pd/TiO_2 的硫耐受性”应用催化 A：概述。

K. Ito, Y. Kogasaka, H, Kurokawa, M. Ohshima, K. Sugiyama, H. Miura: "Preliminary study on mechanism of naphthalene hydrogenation to form decalins via tetralin over Pt/TiO_2"Fuel Processing Technology. 79. 77-80 (2002)

K. Ito、Y. Kogasaka、H、Kurokawa、M. Ohshima、K. Sugiyama、H. Miura：“Pt/TiO_2 上四氢化萘形成萘氢化机理的初步研究”燃料加工技术。