Ru/C催化作用下生物油在超临界乙醇中的提质

doi:10.16085/j.issn.1000-6613.2015.10.020

化工进展 ›› 2015, Vol. 34 ›› Issue (10): 3650-3655.DOI: 10.16085/j.issn.1000-6613.2015.10.020

Ru/C催化作用下生物油在超临界乙醇中的提质

陈文^1,2, 骆仲泱², 杨义², 李国翔², 卢孔裕²

1 广东电网公司电力科学研究院, 广东广州 510080;
2 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:2015-01-26 修回日期:2015-03-12 出版日期:2015-10-05 发布日期:2015-10-05
通讯作者: 骆仲泱,博士,教授,主要从事化石燃料的高效清洁利用理论和能源利用过程中的污染物生成、迁移及控制理论方面的研究。E-mailzyluo@zju.edu.cn。
作者简介:陈文(1988—),男,博士研究生,研究方向为生物油提质改性。E-mailchenwenhuz@zju.edu.cn。
基金资助:
国家自然科学基金(51336008)及国家重点基础研究发展计划(2013CB228100)项目。

Upgrading of bio-oil in supercritical ethanol over Ru/C

CHEN Wen^1,2, LUO Zhongyang², YANG Yi², LI Guoxiang², LU Kongyu²

1 Electric Power Research Institute of Guangdong Power Grid Corporation, Guangzhou 510080, Guangdong, China;
2 State Key Laboratory of Clean Energy Utilizaiton, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2015-01-26 Revised:2015-03-12 Online:2015-10-05 Published:2015-10-05

摘要/Abstract

摘要： 使用了两步加氢-超临界提质以及一步超临界提质两种方法对生物油进行提质,并进行了溶剂回收利用。实验结果表明经过这两种提质方法,生物油的物化性质均得到有效提升,提质后生物油中酸、酮和酚的相对含量明显下降,而醇、醚和酯类等理想产物的相对含量有显著上升。根据每步产物的GC-MS结果,对提质过程中所发生的反应进行了推测。相对于一步法提质所得到生物油,两步提质法所得到的提质生物油中醇和醚类的相对含量略高而酮、酚和酯类的相对含量略低。同时,相比于一步超临界提质,两步加氢-超临界提质过程中乙醇的消耗量有所降低。溶剂的回收利用在降低生物油提质所需要的乙醇含量的同时提高了提质产物中酯类的相对含量,这表明在较低的醇油比条件下超临界提质仍然是一种有效的生物油提质方法。

关键词: 生物油, 催化剂, 超临界, 乙醇

Abstract: To upgrade bio-oil, two upgrading methods were employed:low temperature hydrogenation (175℃) followed by supercritical upgrading in ethanol (HS), and direct upgrading in supercritical ethanol (DS). By both methods, the physical properties (heating value, pH) of bio-oil were improved greatly. Besides, the relative content of acids, ketones, and phenols decreased significantly while that of alcohols/ethers and esters increased dramatically after upgrading. The reactions occurred in each step were tentatively discussed based on GC-MS results. Compared with the upgraded bio-oil from DS, the relative content of alcohols/ethers was higher in that from HS, while the relative content of ketones, phenols, and esters showed an opposite result. The consumption of ethanol was lower in HS. The recovery of ethanol by rotary evaporation and reutilization of the recovered ethanol not only reduced the consumption of ethanol, but also increased the relative content of esters in the upgraded bio-oil. These results indicated that bio-oil could be effectively upgraded by supercritical upgrading at relatively low ratios of ethanol to bio-oil.

Key words: bio-oil, catalyst, supercritical, ethanol

中图分类号:

陈文, 骆仲泱, 杨义, 李国翔, 卢孔裕. Ru/C催化作用下生物油在超临界乙醇中的提质[J]. 化工进展, 2015, 34(10): 3650-3655.

CHEN Wen, LUO Zhongyang, YANG Yi, LI Guoxiang, LU Kongyu. Upgrading of bio-oil in supercritical ethanol over Ru/C[J]. Chemical Industry and Engineering Progree, 2015, 34(10): 3650-3655.

参考文献

[1] Zhang Q,Chang J,Wang T,et al. Review of biomass pyrolysis oil properties and upgrading research[J]. Energy Conversion and Management,2007,48(1):87-92.

[2] Elliott D C. Historical developments in hydroprocessing bio-oils[J]. Energy & Fuels,2007,21(3):1792-1815.

[3] Wildschut J,Mahfud F H,Venderbosch R H,et al. Hydrotreatment of fast pyrolysis oil using heterogeneous noble-metal catalysts[J]. Ind. Eng. Chem. Res.,2009,48(23):10324-10334.

[4] Wildschut J,Iqbal M,Mahfud F H,et al. Insights in the hydrotreatment of fast pyrolysis oil using a ruthenium on carbon catalyst[J]. Energy & Environmental Science,2010,3:962-970.

[5] Elliott D C,Hart T R,Neuenschwander G G,et al. Catalytic hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products[J]. Environmental Progress & Sustainable Energy,2009(3),28:441-449.

[6] Mortensen P M,Grunwaldt J D,Jensen P A,et al. A review of catalytic upgrading of bio-oil to engine fuels[J]. Applied Catalysis A:General,2011,407(1-2):1-19.

[7] Gayubo A G,Valle B,Aguayo A T,et al. Pyrolytic lignin removal for the valorization of biomass pyrolysis crude bio-oil by catalytic transformation[J]. Journal of Chemical Technology & Biotechnology,2010,85(1):132-144.

[8] Gayubo A G,Valle B,Aguayo A T,et al. Olefin production by catalytic transformation of crude bio-oil in a two-step process[J]. Ind. Eng. Chem. Res.,2010,49(1):123-131.

[9] 郑小明,楼辉. 生物质热解油品位催化提升的思考和初步进展[J].催化学报,2009,30(8):765-769.

[10] Zhang Q,Chang J,Wang T,et al. Upgrading bio-oil over different solid catalyst[J]. Energy & Fuels,2006,20(6):2717-2720.

[11] Li X,Gunawan R,Lievens C,et al. Simultaneous catalytic esterification of carboxylic acids and acetalisation of aldehydes in a fast pyrolysis bio-oil from mallee biomass[J]. Fuel,2011,90(7):2530-2537.

[12] Peng J,Chen P,Lou H,et al. Catalytic upgrading of bio-oil by HZSM-5 in sub- and super-critical ethanol[J]. Bioresource Technology,2009,100(13):3415-3418.

[13] Zhao C,He J,Lemonidou A A,et al. Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes[J]. Journal of Catalysis,2011,280(1):8-16.

[14] Li W,Pan C,Sheng L,et al. Upgrading of high-boiling fraction of bio-oil in supercritical methanol[J]. Bioresource Technology,2011,102(19):9223-9228.

[15] Zhang J,Luo Z,Dang Q,et al. Upgrading of bio-oil over bifunctional catalysts in supercritical monoalcohols[J]. Energy & Fuels,2012,26(5):2990-2995.

[16] Dang Q,Luo Z,Zhang J,et al. Experimental study on bio-oil upgrading over catalyst in supercritical ethanol[J]. Fuel,2013,103:683-692.

Ru/C催化作用下生物油在超临界乙醇中的提质

Upgrading of bio-oil in supercritical ethanol over Ru/C

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