Development of the upgrading process of heavy oil in supercritical water

超临界水重油改质工艺开发

• 批准号: 11694121
• 负责人: ARAI Kunio
• 金额: $ 6.98万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11694121/
• 关键词: supercritical water; heavy oil; reforming; partial oxidation; desulfurization; 触媒; in-situ分光; 超臨界二酸化炭素; 劣化; シフト反応; 水素化; 相平衡; 速度

We have developed the new heavy oil upgrading system in supercritical water. In supercritical water, partial oxidation provides effective CO formation, which leads to water gas shift reaction. The hydrogenation of heavy compounds and hydrodesufurization can be expected in partial oxidation without expensive hydrogen or catalyst.We chose the asphalt as a heavy oil model compounds. Supercritical water and supercritical water partial oxidation treatments were applied to the reforming of asphalt. Asphalt was converted at 613 - 673 K, 0 - 0.5 g/cm^3 of water density under argon or air atmosphere. The increase of temperature enhanced the conversion of heavy oils. Under an argon atmosphere and 0.5 g/cm^3 of water density, the asphaltene conversion increased and the sulfur reduction increased with increasing temperature. At 673 K, the asphaltene conversion increased and the yield of CO_2 increased with an increasing water density. Water apparently participated in the reaction and its hydrogen was used for the formation of maltenes. Under an air atmosphere at 673 K, asphaltene conversion was lower but the sulfur reduction was higher than those obtained in argon atmosphere. Experimental results indicate that sulfur moved into the coke.As a result, supercritical water can be an effective solvent for heavy oil conversion. Supercritical water partial oxidation can provide the reaction atmosphere for desulfurization of heavy oils.

我们已经在超临界水中开发了新的重油升级系统。在超临界水中，部分氧化提供了有效的CO形成，从而导致水气体转移反应。在不昂贵的氢或催化剂的情况下，可以预期重型化合物的氢化和氢化剂的氢化。我们选择沥青作为重油模型化合物。超临界水和超临界水部分氧化处理被应用于沥青的改革。沥青以613-673 K，0-0.5 g/cm^3的水密度转化为氩气或空气大气下。温度的升高增强了重油的转化。在氩气气氛和水密度的0.5 g/cm^3下，沥青质转化率增加，硫的减少随温度的升高而增加。在673 K时，沥青质转化率增加，CO_2的产量随水密度的增加而增加。水显然参与了反应，其氢被用于形成麦芽体。在673 K处的空气大气下，沥青质转化率较低，但硫还原比在氩气气中获得的硫降低。实验结果表明硫迁移到可乐中。由于结果，超临界水可能是重油转化的有效溶剂。超临界水部分氧化可以为重油脱硫提供反应气氛。

项目成果

Kunio Arai and Tadafumi Adschiri: "Importance of Phase Equilibria for Understanding Supercritical Fluid Environment"Fluid Phase Equilibria. 158-160. 673-684 (1999)

Kunio Arai 和 Tadafumi Adschiri：“相平衡对于理解超临界流体环境的重要性”流体相平衡。

Adschiri et al.: "Extraction of Taiheiyo Coal with Supereritical Water-HCOOH Mixture"Fuel. 79. 243-248 (2000)

Adschiri 等人：“用超临界水-HCOOH 混合物提取太平洋煤”燃料。

Watanabe et al.: "Develop,emt of a Recycling Proceess for Waste Polyethylene: Pyrolysis of Model Hydrocarbons in the Presence of Supercritical Water"Proceedings of the 1st International Symposium on Feedstock Recycling of Plastics. 215-218 (1999)

Watanabe 等人：“废聚乙烯回收工艺的开发：超临界水存在下模型碳氢化合物的热解”第一届国际塑料原料回收研讨会论文集。

KunioArai,Tadafumi Adschiri,and Masaru Watanabe: ""Hydrogenation of Hydrocarbons through Partial Oxidation in Supercritical Water""Industrial & Engineering Chemistry Research. 39・12. 4697-4701 (2000)

KunioArai、Tadafumi Adschiri、Masaru Watanabe：“通过超临界水的部分氧化进行碳氢化合物的氢化”，工业与工程化学研究 39・12（2000 年）。

M.Watanabe, M.Mochiduki, S.Sawamoto, T.Adschiri, K.Arai: ""Partial oxidation of n-hexadecane and polyethylene in supercritical water""J. Supercritical Fluids. 20. 257-266 (2001)

M.Watanabe、M.Mochiduki、S.Sawamoto、T.Adschiri、K.Arai：“超临界水中正十六烷和聚乙烯的部分氧化”J.