Zn/HZSM-5分子筛催化棕榈油多产芳烃的研究

doi:10.11949/0438-1157.20190424

摘要/Abstract

摘要：

HZSM-5分子筛可用于脂肪酸酯催化转化生产芳烃、低碳烯烃等过程。未经过处理的HZSM-5分子筛芳烃产率较低，使用过渡金属改性后的HZSM-5分子筛酸性质发生了改变，能够提高芳烃的收率。以等体积浸渍法对HZSM-5分子筛进行改性，制备了不同锌含量的 Zn/HZSM-5分子筛，并进行了 XRD、XRF、XPS、NH₃-TPD、SEM、TEM、Py-IR、N₂物理吸附-脱附等多种表征，结果表明锌的引入没有改变 HZSM-5的晶体结构，锌物种能均匀分布在 HZSM-5分子筛表面及孔道。棕榈油催化转化实验结果显示Zn含量（质量分数）为3% 的 Zn/HZSM-5有最好的催化效果，芳烃在液相烃类所占比例（质量分数）为87.92%，芳烃收率（质量分数）为59.44%。

关键词: HZSM-5, Zn改性, 棕榈油, 催化转化, 芳烃

Abstract:

HZSM-5 zeolite can be used in the process of catalytic conversion of fatty acid esters to produce aromatic hydrocarbons and low-carbon olefins. However, the yield of aromatics over untreated HZSM-5 zeolite is low. Modification of HZSM-5 zeolite with transition metal can optimize the acidity and greatly increase the yield of aromatics. A series of Zn/HZSM-5 zeolites with different zinc content were prepared by equal volume impregnation, and the modified zeolites were characterized by XRD, XRF, XPS, NH₃-TPD, SEM, TEM, Py-IR, and N₂physical adsorption-desorption. The results showed that the crystal structure of Zn/HZSM-5 was not changed, and the zinc was uniformly distributed on the surface and pores of HZSM-5 zeolites. Catalytic conversion of palm oil on Zn/HZSM-5 zeolite with Zn content of 3% (mass) showed the best catalytic performance. The content of aromatics in the obtained liquid hydrocarbons was as high as 87.92% (mass), and the yield of aromatics reached 59.44% (mass).

Key words: HZSM-5, Zn modification, palm oil, catalytic conversion, aromatic hydrocarbon

中图分类号:

TE 624

安志远, 朱超, 刘熠斌, 冯翔, 金鑫, 陈小博, 杨朝合. Zn/HZSM-5分子筛催化棕榈油多产芳烃的研究[J]. 化工学报, 2019, 70(11): 4289-4297.

Zhiyuan AN, Chao ZHU, Yibin LIU, Xiang FENG, Xin JIN, Xiaobo CHEN, Chaohe YANG. Catalytic conversion of palm oil to aromatics on Zn/HZSM-5 zeolites[J]. CIESC Journal, 2019, 70(11): 4289-4297.

图/表 14

表1 棕榈油的性质

Table 1 Properties of palm oil

性质	数值
密度(25℃)/(g·cm^-3)	0.88
黏度(40℃)/(mPa·s)	35.41
元素组成（质量分数）/%
C	75.65
H	12.28
O(减差法计算)	15.07
N	<0.1
S	<0.1
主要脂肪酸（质量分数）/%
油酸（C_18:1）	38.8
亚油酸（C_18:2）	10.1
棕榈酸（C_16:0）	43.5
硬脂酸（C_18:0）	4.2

图1 固定床微型反应器装置流程

Fig.1 Flow chart of fixed bed microreactor device

图2 HZSM-5及Zn/HZSM-5的XRD谱图

Fig.2 XRD patterns of HZSM-5 and Zn/HZSM-5 zeolites

图3 Zn/HZSM-5的XPS能谱

Fig. 3 XPS spectra of Zn/HZSM-5 zeolites

图4 Zn/HZSM-5及HZSM-5的NH3-TPD 谱图

Fig.4 NH3-TPD spectra of Zn/HZSM-5 and HZSM-5

表2 HZSM-5及Zn/HZSM-5酸性质分析

Table 2 Analysis of acid properties of HZSM-5 and Zn/HZSM-5 zeolites

分子筛	酸量/( mmol·g^-1)					Strong/Weak	L/B
分子筛	Total	Strong	Weak	B	L	Strong/Weak	L/B
1-Z5	1.25	0.64	0.61	0.87	0.38	1.05	0.44
2-Z5	1.06	0.47	0.59	0.45	0.61	0.8	1.34
3-Z5	1.01	0.33	0.68	0.29	0.72	0.48	2.52
4-Z5	0.95	0.18	0.77	0.15	0.80	0.24	5.3

图5 HZSM-5及Zn/HZSM-5的Py-IR 谱图

Fig.5 Py-IR spectra of HZSM-5 and Zn/HZSM-5 zeolites

图6 HZSM-5及Zn/HZSM-5的N2物理吸附-脱附等温线

Fig.6 N2 physical adsorption-desorption isotherms of HZSM-5 and Zn/HZSM-5 zeolites

表3 HZSM-5及Zn/HZSM-5的表面积和孔结构分析

Table 3 Surface area and pore structure of HZSM-5 and Zn/HZSM-5 zeolites

催化剂	A _BET/ (m²·g^-1)	A _micro/ (m²·g^-1)	V _total/ (cm³·g^-1)	V _micro/ (cm³·g^-1)	d _aver/nm
1-Z5	396	385	0.18	0.16	1.85
2-Z5	385	372	0.18	0.16	1.87
3-Z5	368	353	0.17	0.15	1.90
4-Z5	342	325	0.16	0.14	1.89

图7 HZSM-5及Zn/HZSM-5的SEM图

Fig.7 SEM pictures of HZSM-5 and Zn/HZSM-5 zeolites

图8 HZSM-5及Zn/HZSM-5的TEM图

Fig.8 TEM pictures of HZSM-5 and Zn/HZSM-5

图9 500℃下棕榈油在HZSM-5及Zn/HZSM-5上裂化气体产物收率

Fig.9 Gas yield of catalytic conversion of palm oil on HZSM-5 and Zn/HZSM-5 at 500℃

表4 500℃下棕榈油在HZSM-5及Zn/HZSM-5上的催化产物性质

Table 4 Catalytic product properties of palm oil on HZSM-5 and Zn/HZSM-5 at 500℃

催化剂	液相烃类收率/%	气体收率/%	积炭/%	H₂O/%	液相烃类产物中芳烃含量/%	芳烃收率/%
1-Z5	57.01	32.41	3.84	0.031	91.41	52.10
2-Z5	60.54	28.33	3.68	0.029	92.57	56.04
3-Z5	67.60	23.49	2.40	0.032	87.92	59.44
4-Z5	65.07	24.58	2.63	0.030	86.91	56.55

图10 500℃下棕榈油在HZSM-5及Zn/HZSM-5催化转化芳烃收率

Fig.10 Aromatic hydrocarbon yield for catalytic conversion of palm oil on HZSM-5 and Zn/HZSM-5 at 500℃

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