La改性多级孔HZSM-5在线催化提质生物油

doi:10.16085/j.issn.1000-6613.2018-0791

化工进展 ›› 2019, Vol. 38 ›› Issue (02): 858-866.DOI: 10.16085/j.issn.1000-6613.2018-0791

La改性多级孔HZSM-5在线催化提质生物油

张小雷(),李小华(),邵珊珊(),张瑾,董良秀,胡超,蔡忆昔

1. 江苏大学汽车与交通工程学院，江苏镇江 212013

收稿日期:2018-04-17 修回日期:2018-07-21 出版日期:2019-02-05 发布日期:2019-02-05
通讯作者: 李小华,邵珊珊
作者简介:<named-content content-type="corresp-name">张小雷</named-content>（1993—），男，硕士研究生，研究方向新能源研究。E-mail: <email>1164612719@qq.com</email>。|李小华，教授，硕士生导师，研究方向为发动机工作过程及排放控制与新能源研究。E-mail：<email>lixiaohua@ujs.edu.cn</email>|邵珊珊，副教授，硕士生导师，研究方向为新能源研究。E-mail：<email>shaoshan0810@ujs.edu.cn</email>
基金资助:
国家自然科学基金(51706090);江苏省高等学校自然科学研究重大项目(17KJA470002)

La modified hierarchical porous HZSM-5 catalysts for online upgrading of the pyrolysis vapors from rape straw

Xiaolei ZHANG(),Xiaohua LI(),Shanshan SHAO(),Jin ZHANG,Liangxiu DONG,Chao HU,Yixi CAI

1. Department of Automotive and Traffic Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2018-04-17 Revised:2018-07-21 Online:2019-02-05 Published:2019-02-05
Contact: Xiaohua LI,Shanshan SHAO

摘要/Abstract

摘要：

采用Na₂CO₃溶液对HZSM-5分子筛进行预处理，然后采用浸渍法对预处理后的HZSM-5进行不同负载量的La改性，通过XRD、BET、SEM-EDS和Py-IR等方法对改性前后的HZSM-5进行表征。利用改性前后的HZSM-5在两段式固定床反应器上进行生物质热解产物在线催化实验，对得到的生物油有机相进行理化特性和组成成分分析。结果表明，经过Na₂CO₃溶液处理后，使HZSM-5分子筛形成了含有微-介孔的多级孔孔道结构，La的改性未改变HZSM-5的MFI结构，但改变了分子筛的酸分布。随着La负载量的增加，生物油有机相产率、密度、运动黏度及氧含量先减小后增加，含氧化合物和羰基类化合物含量同样呈现先减小后增加的变化趋势。经过最佳质量分数为5%的La负载后的多级孔HZSM-5分子筛制得的生物油中，有机相高位热值高达37.7 MJ/kg，烃类物质含量达到了49.86%，含氧化合物和羰基类化合物含量分别减少了32.43%和57.03%。

关键词: HZSM-5分子筛, 多级孔, 镧, 生物油, 催化提质

Abstract:

To improve the characteristics of the bio-oil, La modified HZSM-5 with hierarchical structure was applied in the catalytic pyrolysis of biomass. First, the HZSM-5 zeolite was pretreated with Na₂CO₃ solution, and then the pretreated HZSM-5 was modified with different loadings of La by impregnation. The modified HZSM-5 were characterized by XRD, BET, SEM-EDS and Py-IR, respectively. The catalysts were used in the process of preparing bio-oil and the bio-oil organic phases were studied from the aspects of composition and physical properties. The results showed that the modified HZSM-5 catalysts formed micro/meso-porous pore structure and retained typical MFI topology structure. But the modification of La changed the acid distribution of the zeolite. With the increase of loadings of La, the yield, density, kinematic viscosity and oxygen content of bio-oil organic phase decreased first and then increased, while the content of oxygenated compounds and carbonyl compounds showed the same tendency as well. The hierarchical porous HZSM-5(La loading were 5%) catalyst had a better effect on the removal of aldehyde and ketone contained in the bio-oil organic phase which improved the stability of the bio-oil, the oxygenated compounds and the carbonyl compounds decreased by 32.43% and 57.03%, respectively. Meanwhile, the hydrocarbon content and the higher heating value of the bio-oil organic phase reached 49.86% and 37.7MJ/Kg, respectively.

Key words: HZSM-5 zeolite, hierarchical porous, La, bio-oil, catalytic upgrading

中图分类号:

TK6
TQ35

张小雷, 李小华, 邵珊珊, 张瑾, 董良秀, 胡超, 蔡忆昔. La改性多级孔HZSM-5在线催化提质生物油[J]. 化工进展, 2019, 38(02): 858-866.

Xiaolei ZHANG, Xiaohua LI, Shanshan SHAO, Jin ZHANG, Liangxiu DONG, Chao HU, Yixi CAI. La modified hierarchical porous HZSM-5 catalysts for online upgrading of the pyrolysis vapors from rape straw[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 858-866.

图/表 9

图1 HZSM-5和改性HZSM-5的XRD谱图

图2 改性前后HZSM-5的N2吸附-脱附等温线和孔径分布

图3 HZSM-5和改性HZSM-5的SEM图

图4 HZSM-5和改性HZSM-5的EDS图

图5 HZSM-5和改性HZSM-5的Py-FTIR谱图和酸量分布

图6 使用不同催化剂后各相产率分布

表1 使用不同催化剂后得到的生物油理化特性

催化剂	密度 /g·cm^-3	pH	运动黏度 /mm²·s^-1	高位热值 /MJ·kg^-1	C^②/%	H^②/%	O^③/%
Y0	1.18	2.10	8.85	28.44	59.95	9.14	30.91
Y1	0.93	5.17	6.01	31.52	70.65	8.51	20.82
Y2	0.95	5.94	5.81	35.30	77.59	8.03	14.37
Z1	0.96	5.86	5.80	33.35	76.09	8.22	15.68
Z2	0.94	6.01	5.64	37.70	78.52	8.01	13.47
Z3	0.96	5.95	5.74	34.35	77.51	8.25	14.24
Z4	0.98	5.82	5.79	33.67	75.72	8.37	15.90
柴油	0.84	nd^①	3~8(20℃)	45.50	86.58	13.29	0.01

图7 改性HZSM-5催化后生物油有机相中烃类化合物分布和烃类中碳原子分布

图8 改性HZSM-5催化后生物油有机相中含氧化合物分布和含氧化合物中氧原子分布

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La改性多级孔HZSM-5在线催化提质生物油

La modified hierarchical porous HZSM-5 catalysts for online upgrading of the pyrolysis vapors from rape straw

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