Preparation of La modified Cu/Zn/Al catalysts and its properties for catalytic liquefaction of cellulose

doi:10.16085/j.issn.1000-6613.2016.s1.030

Chemical Industry and Engineering Progree ›› 2016, Vol. 35 ›› Issue (S1): 179-187.DOI: 10.16085/j.issn.1000-6613.2016.s1.030

• Industrial catalysis • Previous Articles Next Articles

Preparation of La modified Cu/Zn/Al catalysts and its properties for catalytic liquefaction of cellulose

MA Yiwen^1,2, BAO Guirong^1,2, WANG Qingqing^1,2, LI Fashe^1,2

1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan, China;
2. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China

Received:2016-01-19 Revised:2016-05-05 Online:2016-07-08 Published:2016-06-30

La改性Cu/Zn/Al催化剂的制备及其催化纤维素液化性能

马依文^1,2, 包桂蓉^1,2, 王青青^1,2, 李法社^1,2

1. 昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室, 云南昆明 650093;
2. 昆明理工大学冶金与能源工程学院, 云南昆明 650093

通讯作者: 包桂蓉,教授,主要从事工程热物理、生物质的超临界流体转化方面的研究。E-mail baoguirong@hotmail.com。
作者简介:马依文(1991-),女,硕士研究生,主要从事催化剂制备研究、纤维素在超临界甲醇中催化液化。
基金资助:
国家自然科学基金项目(51266003)。

Abstract

Abstract: Different content of lanthanum modified Cu/Zn/Al catalysts were prepared by coprecipitation method.The effects of lanthanum on catalyst performance were illuminated by using TG-DTG, XRD, BET, H₂-TPR techniques, the results showed that lanthanum can promote the active component dispersed on the surface of the carrier and maintain the pore structure of the catalyst.The moderate amount of La could promote the combination of the two phases of CuO and ZnO, also can increase the density of the active center.But excess lanthanum would cause changes in performance of the catalyst which led to the reduce of the catalyst activity.Direct liquefaction micro-crystalline cellulose (MCC) over La modified Cu/Zn/Al catalyst in supercritical methanol, and study on influence of conversion and liquefied products with different contents of La.It was found that addition of La can effectively improve the conversion rate of MCC and yield of alcohols.The liquefaction products were detected by GC-MS and showed the main component of liquefied product were alcohols, esters, aldehydes, ketones and alkanes.The addition of La can improved the selectivity of alcohols product.The experimental results from single-factor experiment showed the optimum liquefaction conditions were reaction temperature 320℃, reaction time 75min, 75% dosage of catalyst.

Key words: microcrystalline cellulose, supercritical fluid, catalytic liquefaction, catalyst

摘要： 采用共沉淀法制备了不同La含量改性Cu/Zn/Al的催化剂,通过热重分析(TG/DTG)、X射线衍射(XRD)、比表面积测定(BET)、H₂程序升温还原(H₂-TPR)等表征手段对改性催化剂进行评价,分析结果表明,La助剂能够促进活性组分在载体表面的分散,很好地维持了催化剂的孔结构,适量助剂La的添加可促进CuO、ZnO两相间相互融合,增加活性中心的分散度,使CuO更加易于还原,但过多的La含量会使催化剂的性能发生改变,导致催化剂的活性降低。在超临界甲醇中使用La改性Cu/Zn/Al催化剂催化液化微晶纤维素,发现添加少量的La可有效地提高催化液化效果,相较于为添加助剂的Cu/Zn/Al催化剂,MCC转化率与醇类收率都得到了明显的提高。通过GC-MS分析,可以得到液化产物主要有醇类、酯类、酮类、醛类、烷烃等物质,添加助剂后提高了醇类产物的选择性。设置单因素实验,可知改性后Cu_1.2Zn_4.8Al_1.9La_0.1催化剂的最佳反应条件为:反应温度320℃,反应时间75min,催化剂用量75%。

关键词: 微晶纤维素, 超临界流体, 催化液化, 催化剂

CLC Number:

MA Yiwen, BAO Guirong, WANG Qingqing, LI Fashe. Preparation of La modified Cu/Zn/Al catalysts and its properties for catalytic liquefaction of cellulose[J]. Chemical Industry and Engineering Progree, 2016, 35(S1): 179-187.

马依文, 包桂蓉, 王青青, 李法社. La改性Cu/Zn/Al催化剂的制备及其催化纤维素液化性能[J]. 化工进展, 2016, 35(S1): 179-187.

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Preparation of La modified Cu/Zn/Al catalysts and its properties for catalytic liquefaction of cellulose

La改性Cu/Zn/Al催化剂的制备及其催化纤维素液化性能

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