CIESC Journal ›› 2014, Vol. 65 ›› Issue (8): 3004-3011.DOI: 10.3969/j.issn.0438-1157.2014.08.022

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Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO2 catalyst

ZHANG Liang1, WU Man1, YANG Ya1, ZHANG Xiuli1, XU Xiufeng2, GUO Qingjie1   

  1. 1 Key Laboratory of Clean Chemical Processing of Shandong Province, College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China;
    2 Institute of Applied Catalysis, Yantai University, Yantai 264005, Shandong, China
  • Received:2013-11-22 Revised:2014-03-12 Online:2014-08-05 Published:2014-08-05
  • Supported by:

    supported by the Special Fund of Marine Renewable Energy (GHME2001SW02).

小球藻热解油在Ni-Cu/ZrO2催化剂上的加氢脱氧

张亮1, 吴曼1, 杨雅1, 张秀丽1, 徐秀峰2, 郭庆杰1   

  1. 1 青岛科技大学化工学院, 清洁化工过程山东省高校重点实验室, 山东 青岛 266042;
    2 烟台大学应用催化研究所, 山东 烟台 264005
  • 通讯作者: 郭庆杰
  • 基金资助:

    海洋可再生能源专项资金项目(GHME2001SW02)。

Abstract: The catalytic hydrodeoxygenation of bio-oil obtained by fast pyrolysis of chlorella over Ni-Cu/ZrO2 catalyst was carried out in a fixed-bed reactor to improve the quality of the bio-oil. The catalysts were characterized by XRD, H2-TPR, TG and NH3-TPD techniques. The results showed that the addition of Cu promoted dispersion of active species, and increased catalytic hydrodeoxygenation activity of Ni-Cu/ZrO2 catalysts. However, the activity went up first, and then went down with increase of Cu loading. A possible theoretical explanation was also given. At reaction conditions of 2 MPa and 350℃, the performance of Ni-Cu/ZrO2 catalyst was stable and it made the oxygen content in the bio-oil decreased sharply. For the Ni-Cu/ZrO2 catalyst with Cu/Ni mass ratio of 0.40, the efficiency of oxygen removal was 82.0% after 3 h reaction and larger than 77.0% after 24 h reaction. The heat value of upgraded bio-oil increased from 31.5 MJ·kg-1 to 35.0 MJ·kg-1, while the kinetic viscosity at 40℃ fell from 20.5 mm2·s-1 to 9.5 mm2·s-1 after hydrodeoxygenation reaction. In addition, the water in upgraded bio-oil could be removed easily. Furthermore, the stability of upgraded bio-oil was improved significantly due to the reduction of unstable acids.

Key words: bioenergy, fix-bed, catalyst, bio-oil, hydrodeoxygenation reaction

摘要: 在小型固定床反应器中以Ni-Cu/ZrO2为催化剂,对小球藻热解油进行催化加氢脱氧,以改善生物油性能。利用XRD、H2-TPR、TG、NH3-TPD等技术对催化剂进行了结构表征。结果表明,Cu的加入有效促进了Ni-Cu/ZrO2催化剂活性相的表面分散,提高了该催化剂对小球藻热解油加氢脱氧反应的催化活性。在2 MPa、350 ℃反应条件下,随Cu/Ni的增大,Ni-Cu/ZrO2的催化活性先升高后降低,Cu/Ni质量比为0.40时的催化性能最好,连续运行3 h后所得精制生物油脱氧率达82.0%。Ni-Cu/ZrO2催化剂在反应过程中,表面结焦少,活性粒子及催化剂性能稳定,连续运行24 h后所得精制生物油脱氧率依然维持在77.0%以上。小球藻热解油经催化加氢脱氧所得的精制生物油,低位热值由31.5 MJ·kg-1提高至35.0 MJ·kg-1,40℃运动黏度由20.5 mm2·s-1降至9.5 mm2·s-1,且油品中水分更易于脱除。精制生物油中高级脂肪酸的含量减少,油品稳定性大幅提高。

关键词: 生物能源, 固定床, 催化剂, 生物油, 加氢脱氧

CLC Number: