催化学报

催化学报 ›› 2014, Vol. 35 ›› Issue (5): 709-722.DOI: 10.1016/S1872-2067(14)60046-2

• 研究论文 • 上一篇    下一篇

生物油酸酮类模化物与乙醇在HZSM-5上共裂化制备生物汽油

王树荣, 蔡勤杰, 王相宇, 张力, 王誉蓉, 骆仲泱   

  1. 浙江大学能源清洁利用国家重点实验室, 浙江杭州310027
  • 收稿日期:2013-12-05 修回日期:2014-01-22 出版日期:2014-04-18 发布日期:2014-04-24
  • 通讯作者: 王树荣
  • 基金资助:

    国家自然科学基金（51276166）；国家重点基础研究发展计划（973计划，2013CB228101）； “十二五”国家科技支撑计划（2011BAD22B06）；浙江省杰出青年科学基金（R1110089）；新世纪优秀人才支持计划（NCET-10-0741）.

Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5

Shurong Wang, Qinjie Cai, Xiangyu Wang, Li Zhang, Yurong Wang, Zhongyang Luo   

  1. State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2013-12-05 Revised:2014-01-22 Online:2014-04-18 Published:2014-04-24
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (51276166), the National Basic Research Program of China (973 Program, 2013CB228101), the National Science and Technology Supporting Plan Through Contract (2011BAD22B06), Zhejiang Provincial Natural Science Foundation of China (R1110089), and the Program for New Century Excellent Talents in University (NCET-10-0741).

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摘要：

生物油中酸类和酮类化合物具有较高的裂化活性，而使用分子蒸馏技术能将这些组分富集到蒸出馏分中，因此蒸出馏分相比原始生物油具有更好的裂化特性. 为了模拟实际蒸出馏分的组成，本文将生物油模化物（羟基丙酮（HPO）、环戊酮和乙酸）进行配比混合，在固定床反应器上对其与乙醇的共裂化行为进行了研究，考察了不同反应温度和压力对混合反应物的转化率、粗汽油相的选择性和组成的影响. 研究发现，当反应温度在340 ℃时，乙酸和乙醇的转化率分别仅为67.9%和74.4%，同时得到的油相产物中烃类含量仅为59.8%，并含有大量的含氧副产物. 常压裂化同样生成了低品质的油相产物，同时油相选择性仅为10.8%. 提高反应温度能促进反应物的转化，提高裂化过程中的脱氧效率，而提高反应压力对液体烃类的生成有明显的促进作用. 在400 ℃和2 MPa时，酸类和酮类都有良好的裂化表现，反应物接近完全转化，粗汽油相选择性达到31.5%，且全部由烃类组成，其中芳香烃含量高达91.5%. 此外，反应后催化剂表征和稳定性测试结果表明，催化剂在较长时间反应后会失活，但通过催化剂再生能够很好地恢复催化剂活性.

关键词: 生物油, 分子蒸馏, 混合模化物, 催化裂化, 生物汽油

Abstract:

Acids and ketones in biomass pyrolysis oil (bio-oil) can be readily cracked to produce hydrocarbons. They can also be enriched in the distilled fraction using molecular distillation techniques. To simulate the actual composition of the distilled fraction, the co-cracking performance of mixtures of hydroxypropanone, cyclopentanone, and acetic acid with ethanol in a fixed-bed reactor over an HZSM-5 catalyst was studied. The influences of reaction temperature and pressure on the reactant conversion, selectivity, and composition of the oil phase were investigated. At a low reaction temperature of 340 ℃, the conversions of acetic acid and ethanol were as low as 67.9% and 74.4%, respectively, and the oil phase had a low hydrocarbon content of 59.8%, with large amounts of oxygenated byproducts. Cracking under atmospheric pressure also generated a low-quality oil phase with a very low selectivity of only 10.8%. Increasing the reaction temperature promoted reactant conversion and improved the deoxygenation efficiency, whereas increasing the reaction pressure significantly promoted hydrocarbon production. The optimum conditions for biogasoline production were 400 ℃ and 2 MPa. Under these conditions, the reactant conversion reached 100% and the oil phase selectivity was 31.5 wt%. This oil phase consisted entirely of hydrocarbons, 91.5 wt% of which were aromatic hydrocarbons, indicating that the HZSM-5 catalyst had high activity for deoxygenation and aromatization reactions during cracking. In addition, characterization of the spent catalysts and stability tests showed that the catalyst was deactivated after a long reaction time. However, the catalytic activity was recovered by catalyst regeneration.

Key words: Bio-oil, Molecular distillation, Mixed-model compound mixtures, Co-cracking, Bio-gasoline