合成气制低碳烯烃串联反应中Zn-Al氧化物的制备及性能

李保珍; 孟凡会; 王丽娜; 李忠

doi:10.19906/j.cnki.JFCT.2022049

合成气制低碳烯烃串联反应中Zn-Al氧化物的制备及性能

doi: 10.19906/j.cnki.JFCT.2022049

太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024

基金项目: 山西省自然科学基金（202103021224073）和山西省重点研发计划(国际科技合作)(201803D421011)资助

详细信息

通讯作者:
Tel: 0351-6018526, E-mail: mengfanhui@tyut.edu.cn

lizhong@tyut.edu.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2022-05-20
- 修回日期: 2022-06-11
- 录用日期: 2022-06-16
- 网络出版日期: 2022-09-26
- 刊出日期: 2023-01-10

Study on preparation and catalytic performance of Zn-Al oxides for tandem reaction of syngas conversion into light olefins

Taiyuan University of Technology, State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan 030024, China

Funds: The project was supported by the Natural Science Foundation of Shanxi Province (202103021224073) and the Key Research and Development Project of Shanxi Province (201803D421011)

摘要

摘要: 以工业拟薄水铝石为铝源，通过微波辅助蒸发诱导自组装（M-EISA）法制备了一系列不同Zn/Al原子比的Zn-Al氧化物，并与SAPO-18分子筛物理混合后考察其催化合成气制低碳烯烃（${\rm{C}}_2^= -{\rm{C}}_4^=$）反应性能。采用X射线衍射（XRD）、透射电镜（TEM）、N₂吸附-脱附、CO和H₂程序升温脱附（CO-TPD、H₂-TPD）、X射线光电子能谱（XPS）等进行表征。M-EISA法制备的Zn-Al氧化物随Zn/Al原子比的增加，比表面积和孔容逐渐下降，平均孔径先增大后降低。与浸渍（IP）法制备的ZnAl-IP相比，Zn/Al原子比为1∶2的ZnAl₂O_x样品中Zn分散度高，形成的ZnAl₂O₄尖晶石结构产生了更多的氧空位。催化结果表明，M-EISA法制备的Zn-Al样品活性随Zn/Al原子比的增加而先增加后减小，${\rm{C}}_2^= -{\rm{C}}_4^= $选择性逐渐降低。ZnAl₂O_x样品的CO转化率最高（34.8%），且反应50 h未见明显失活，催化性能明显优于ZnAl-IP样品。
- 合成气转化 /
- 低碳烯烃 /
- Zn-Al氧化物 /
- 双功能催化剂 /
- 微波辅助蒸发诱导自组装法
Abstract: A series of Zn-Al oxides with different Zn/Al atomic ratios were prepared by the microwave-assisted evaporation-induced self-assembly (M-EISA) method, using industrial pseudo-boehmite as aluminum source. The prepared Zn-Al oxides were physically mixed with SAPO-18 zeolite and applied in tandem reaction for direct conversion of syngas to light olefins (${\rm{C}}_2^= -{\rm{C}}_4^= $). X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption, CO and H₂ temperature-programmed desorption (CO-TPD, H₂-TPD) and X-ray photoelectron spectroscopy (XPS) were selected for characterization. As the increase of Zn/Al ratio, the specific surface area and pore volume of Zn-Al oxides gradually decreased, while the average pore diameter firstly increased and then decreased. Compared with the ZnAl-IP prepared by the impregnation (IP) method, the ZnAl₂O_x with the Zn/Al ratio of 1∶2 had a high dispersion of Zn and formed the ZnAl₂O₄ spinel structure that produced more oxygen vacancies. The catalytic results showed that the activity of Zn-Al samples prepared by M-EISA method firstly increased and then decreased as the Zn/Al ratio rose, while the ${\rm{C}}_2^= -{\rm{C}}_4^= $ selectivity gradually decreased. ZnAl₂O_x sample exhibited the highest CO conversion of 34.8% and almost no obvious deactivation after 50 h reaction, furthermore, its catalytic performance was much better than that of ZnAl-IP sample.
- syngas conversion /
- light olefins /
- Zn-Al oxide /
- bifunctional catalyst /
- microwave-assisted evaporation-induced self-assembly method

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图 1 不同Zn-Al氧化物XRD谱图及ZnAl₂O_x氧化物的原位XRD谱图

Figure 1 (a) XRD patterns of different Zn-Al oxides; (b) in-situ XRD patterns of ZnAl₂O_x oxides treated by H₂ at different temperatures and time

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图 2 不同Zn-Al氧化物的TEM及HR-TEM照片

Figure 2 TEM and HR-TEM images of different Zn-Al oxides((a), (b)): ZnAl₂O_x; ((c), (d)): ZnAl₅O_x; ((e), (f)): ZnAl-IP

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图 3 不同Zn-Al氧化物的N₂吸附-脱附等温线

Figure 3 N₂ adsorption-desorption isotherms of different Zn-Al oxides

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图 4 不同Zn-Al氧化物的化学吸附曲线

Figure 4 TPD profiles of different Zn-Al oxides(a): CO-TPD; (b): H₂-TPD; (c): CO and H₂ TPD profiles in the temperature range of 180−400 ℃ and hold at 400 ℃ for 40 min

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图 5 Zn-Al氧化物的H₂-TPR谱图

Figure 5 H₂-TPR profiles of Zn-Al oxides

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图 6 ZnAl₂O_x及ZnAl-IP氧化物的（a）O 1s XPS谱图和（b）EPR谱图

Figure 6 (a) O 1s XPS spectra and (b) EPR spectra of ZnAl₂O_x and ZnAl-IP oxides

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图 7 ZnAl₂O_x及ZnAl-IP与SAPO-18结合后催化STO反应的稳定性

Figure 7 Catalytic stability of ZnAl₂O_x and ZnAl-IP combined with SAPO-18 for STO reaction (a): ZnAl₂O_x/SAPO-18; (b): ZnAl-IP/SAPO-18

Reaction condition: 400 ℃, 2.5 MPa, 5000 mL/(g_cat·h), weight ratio of Zn-Al to SAPO-18(0.1) is 3∶1，30−60 mesh

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表 1 不同Zn-Al氧化物的织构性质

Table 1 Textural properties of different Zn-Al oxides

Sample	S_BET^a/(m²·g⁻¹)	v_total^b/(cm³·g⁻¹)	d_average^c/nm
Al₂O₃	196	0.55	7.2
ZnAl-IP	111	0.30	7.0
ZnAl₅O_x	126	0.85	19.1
ZnAl₃O_x	89	0.70	21.4
ZnAl₂O_x	74	0.63	23.5
ZnAl₁O_x	63	0.56	23.4
ZnAl_0.5O_x	52	0.34	18.8
^a: Calculated by the BET equation, ^b: BJH desorption pore volume, ^c: BJH desorption average pore diameter

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表 2 不同Zn-Al氧化物的CO和H₂脱附量

Table 2 Amounts of desorbed CO and H₂ of different Zn-Al oxides

Sample	Amounts of desorbed CO and H₂/(μmol·g⁻¹)
Sample	^a CO	^b H₂	^c CO	^c H₂
ZnO	15.7	−		−
ZnAl_0.5O_x	165.8	78.2		−
ZnAl₂O_x	311.6	100.9	148.7	53.1
ZnAl₅O_x	359.7	141.7		−
Al₂O₃	355.7	139.2		−
ZnAl-IP	272.5	120.4	96.4	36.7
^a: obtained from Figure 4(a),^b: obtained from Figure 4(b), ^c: obtained from Figure 4(c)

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表 3 不同Zn-Al氧化物与SAPO-18结合后催化STO的反应性能

Table 3 Catalytic performance of different Zn-Al oxides combined with SAPO-18 for STO reaction

Metal oxides	CO conv. /%	Hydrocarbons distribution /%				CO₂ sel. /%	STY / （mL·g$^{- {1} }_{ {\rm{cat} } }$·h⁻¹）
Metal oxides	CO conv. /%	CH₄	${\rm{C} }_{2}^= -{\rm{C} }_{4}^=$	${\rm{C} }_{2}^{0} -{\rm{C} }_{4}^{0}$	C_{5 +}	CO₂ sel. /%	STY / （mL·g$^{- {1} }_{ {\rm{cat} } }$·h⁻¹）
Al₂O₃	2.4	53.4	19.0	22.4	5.3	38.3	3.8
ZnAl₅O_x	16.2	7.5	74.7	12.8	5.1	45.7	88.7
ZnAl₃O_x	32.7	8.3	73.0	14.2	4.5	43.1	183.4
ZnAl₂O_x	34.8	9.0	70.7	15.3	5.0	43.9	186.3
ZnAl₁O_x	27.7	11.2	63.3	21.6	4.0	47.2	125.0
ZnAl_0.5O_x	23.8	12.2	62.1	21.2	4.6	44.8	110.1
ZnAl-IP	14.9	14.9	60.2	19.6	5.3	45.0	66.6
Reaction conditions: 400 ℃, 3.0 MPa, 4500 mL/(g_cat·h), weight ratio of oxides to SAPO-18(0.1) = 2∶1, the data were acquired after a 12 h reaction on stream

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