Novbel Desulfurization, Denitrogenation, and Demetalation Process for Fuel Oils Effected by Photochemical Reactions

新型光化学反应燃料油脱硫、脱氮、脱金属工艺

• 批准号: 12555215
• 负责人: HIRAI Takayuki
• 金额: $ 8.26万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12555215/
• 关键词: Fuel oils; Desulfurization; Denitrogenation; Demetalation; Photochemical reaction; Chemical conversion; Upgrading; Clean Fuel; 液液抽出法

Sulfur-, nitrogen-, and metal-containing compounds, present in fuel oils, are causes of air pollution and corrosion of combustion engine. These are removed presently by catalytic hydrorefining process. The present work developed novel desulfurization, denitrogenation, and demetalation processes, based on photochemicalconversion of the objective species.1. Photochemical Desulfurization and Denitrogenation. Novel desulfurization and denitrogenation processes for heavy-middle distillate (light oils and vacuum gas oil), based on photoirradiation of oil/water and oil/acetonitrile systems, where sulfur and nitrogen compounds are photooxidized and removed successfully from oil. Alkyl-substituted DBTs, which is difficult to desulfurize by current hydrorefining process, is desulfurized easily by the present processes, and deep desulfurization is achieve successfully.2. Photochemical Demetalation. Photochemical demetalation process for residue oils is developed based on photodecomposition of van … More adyl- and nickelporphyrins by UV irradiation in the presence of 2-propanol and subsequent extraction of the resulting metals by aqueous HC1 solution. By employing the process, almost all of the vanadium and nickel in atmospheric and vacuum residue oils can be removed successfully.3. Desulfurization and Denitrogenation Based on Sulfonium Salts Formation. Novel desulfurization process for oils, based on alkylation of sulfur compounds and the subsequent precipitation of the resulting sulfonium salts, is developed. The sulfur content of light oil is decreased successfully to less than 0.005 wt % (ultra deep desulfurization level), where nitrogen compounds are also removed simultaneously.4. Desulfurization Based on Sulfimides Formation. Novel desulfurization process for light oil, based on imidation of sulfur compounds and the subsequent adsorption of the resulting sulfimides, is developed.5. Desulfurization and Denitrogenation Based on Chemical Oxidation. Novel desulfurization and denitrogenation process for light oil, based on chemical oxidation of sulfur and nitrogen compounds using hydrogen peroxide and acetic acid and the subsequent extraction of the resulting materials by aqueous acetonitrile solution, is developed. Less

燃油中存在的含硫、含氮和金属化合物是造成空气污染和内燃机腐蚀的原因。这些目前通过催化加氢精制工艺除去。目前的工作基于目标物质的光化学转化，开发了新的脱硫、脱氮和脱金属工艺。1．光化学脱硫脱氮。基于油/水和油/乙腈系统的光辐照的重质中间馏分油（轻油和减压瓦斯油）的新型脱硫和脱氮工艺，其中硫和氮化合物被光氧化并成功地从油中去除。现有加氢精制工艺难以脱硫的烷基取代二苯并噻吩(DBTs)，采用本工艺可以轻松脱硫，并成功实现深度脱硫。 2．光化学脱金属。渣油光化学脱金属工艺是基于在 2-丙醇存在下通过紫外线照射对芳基卟啉和镍卟啉进行光分解，然后用 HCl 水溶液萃取所得金属而开发的。采用该工艺可成功脱除常减压渣油中几乎全部的钒、镍。 3．基于锍盐形成的脱硫脱氮。开发了基于硫化合物烷基化和随后所得锍盐沉淀的新型油脱硫工艺。成功将轻油硫含量降至0.005wt%以下（超深度脱硫水平），同时脱除氮化合物。 4．基于硫酰亚胺形成的脱硫。开发了基于硫化合物酰亚胺化和随后吸附所得硫酰亚胺的轻质油脱硫新工艺。 5．基于化学氧化的脱硫脱氮。开发了一种新的轻油脱硫脱氮工艺，该工艺基于使用过氧化氢和乙酸对硫和氮化合物进行化学氧化，然后用乙腈水溶液萃取所得材料。较少的

项目成果

Y. Shiraishi, T. Naito, T. Hirai and I. Komasawa: "A Novel Methodology Towards Deep Desulfurizatio of Light Oil Effected by Sulfimides Formation"Chem. Commun.. 1256-1257 (2001)

Y. Shiraishi、T. Naito、T. Hirai 和 I. Komasawa：“一种通过硫酰亚胺形成实现轻质油深度脱硫的新方法”Chem。

Y. Shiraishi, K. Tachibana, T. Hirai and I. Komasawa: "A Novel Desulfurization Process for Fuel Oils Based on the Formation and Subsequent Precipitation of S-Alkylsulfonium Salts. 5. Denitrogenation Reactivity of Basic and Neutral Nitrogen Compounds"Ind.

Y. Shiraishi、K. Tachibana、T. Hirai 和 I. Komasawa：“基于 S-烷基锍盐的形成和随后沉淀的新型燃料油脱硫工艺。5. 碱性和中性氮化合物的脱氮反应性”Ind。

Y. Shiraishi, T. Hirai and I. Komasawa: "Novel Desulfurization and Simultaneous Denitrogenation Processes for Fuel Oils by Alkylation and Precipitation"Kagaku Kogaku Ronbunshu. 28(3). 231-240 (2002)

Y. Shiraishi、T. Hirai 和 I. Komasawa：“通过烷基化和沉淀对燃料油进行新型脱硫和同时脱氮工艺”Kagaku Kogaku Ronbunshu。

Y. Shiraishi, K. Tachibana, T. Hirai and I. Komasawa: "Desulfurization and Denitrogenation Procdess for Light Oils Based on Chemical Oxidation followed by Liquid-Liquid Extraction"Ind. Eng. Chem. Res.. 41(17). 4362-4375 (2002)

Y. Shiraishi、K. Tachibana、T. Hirai 和 I. Komasawa：“基于化学氧化和液液萃取的轻质油脱硫脱氮工艺”Ind。

Y. Shiraishi, T. Hirai and I. Komasawa: "S-Methylsulfonium Salts Obtained by Desulfurization of Vacuum Gas Oil and Catalytic-Cracked Gasoline as Thermal Latent Polymerization Initiator"J. Chem. Eng. Japan. 36(3)(in press). (2003)

Y. Shiraishi、T. Hirai 和 I. Komasawa：“通过减压瓦斯油和催化裂化汽油脱硫获得的 S-甲基锍盐作为热潜聚引发剂”J。