小球藻热解油在Ni-Cu/ZrO_2催化剂上的加氢脱氧  

Catalytic hydrodeoxygenation of fast pyrolysis bio-oil of chlorella over Ni-Cu/ZrO_2 catalyst

作　　者：张亮[1] 吴曼[1] 杨雅[1] 张秀丽[1] 徐秀峰[2] 郭庆杰[1] 

机构地区：[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

出　　处：《化工学报》2014年第8期3004-3011,共8页CIESC Journal

基　　金：海洋可再生能源专项资金项目(GHME2001SW02)~~

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。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＆amp;nbsp;bio-oil was improved significantly due to the reduction of unstable acids.

关 键 词：生物能源 固定床 催化剂 生物油 加氢脱氧 

分 类 号：TK6[动力工程及工程热物理—生物能]