Influence of the SiO2/Al2O3 ratio on the performance of USY zeolites for the gas-phase dehydration of glycerol to acrolein

doi:10.16085/j.issn.1000-6613.2018-1897

Abstract

Abstract:

The USY zeolites with different SiO₂/Al₂O₃ ratios were prepared from commercial USY zeolites via the ammonium exchange and hydrothermal treatment and then were characterized by XRD, SEM, N₂ adsorption and desorption isotherms and py-IR. The influence of SiO₂/Al₂O₃ ratio on the performance of USY zeolites for the gas-phase dehydration of glycerol to acrolein was investigated. The results of XRD and SEM showed that the ammonium exchange and hydrothermal treatment only increased the SiO₂/Al₂O₃ ratio and decreased the relative crystallinity of USY but had no effect on the structure and morphology of USY. The analysis of N₂ adsorption and desorption isotherms and py-IR demonstrated that the total and B acid content of the USY gradually decreased, L acid content, mesoporous volume and mean pore size increased with the increase of framework SiO₂/Al₂O₃ ratio. Activity evaluation results revealed that the textural property had more important effect on glycerol conversion and acrolein selectivity than the acid property. Therefore, USY with a SiO₂/Al₂O₃ ratio of 29 displayed the best catalytic performance, giving an acrolein yield of 51.8% and glycerol conversion of 84.5%.

Key words: USY zeolite, framework SiO₂/Al₂O₃ ratio, catalysis, glycerol, acrolein

摘要：

以铵交换和高温水热处理法制备了不同硅铝比的超稳Y型分子筛（USY），利用X射线衍射、扫描电镜、氮气吸附脱附和吡啶红外等技术对USY进行了表征。以USY为催化剂，考察了USY的骨架硅铝比对气相甘油脱水制丙烯醛的影响。X射线衍射和扫描电镜结果表明，铵交换和高温水热处理只是提高USY的硅铝比，相对结晶度略有降低，而对Y型分子筛的结构和形貌没有影响。氮气吸附-脱附和吡啶红外结果表明，随USY骨架SiO₂/Al₂O₃比提高，总酸量和B酸酸量逐渐降低，L酸酸量有所增多，介孔孔体积和平均孔径有所增大。气相甘油脱水反应结果表明，催化剂织构性质对甘油转化率和丙烯醛选择性的影响大于酸性的影响，因而SiO₂/Al₂O₃比为29的USY催化剂的反应性能最好，甘油转化率和丙烯醛收率分别达到了84.5%和51.8%。

关键词: 超稳Y型分子筛, 骨架硅铝比, 催化, 甘油, 丙烯醛

CLC Number:

TQ224.23

Qi HAN, Haiyan LI, Ying YANG, Baijun LIU. Influence of the SiO₂/Al₂O₃ ratio on the performance of USY zeolites for the gas-phase dehydration of glycerol to acrolein[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2791-2795.

韩琪, 李海岩, 杨英, 刘百军. 超稳Y型分子筛的骨架硅铝比对甘油气相脱水反应的影响[J]. 化工进展, 2019, 38(06): 2791-2795.

Figures/Tables 9

References 16

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样品	相对结晶度/%	骨架硅铝比（SiO₂/Al₂O₃）
USY-14	109	13.9
USY-19	100	19.2
USY-23	96	23.4
USY-29	85	28.6

样品	相对结晶度/%	骨架硅铝比（SiO₂/Al₂O₃）
USY-14	109	13.9
USY-19	100	19.2
USY-23	96	23.4
USY-29	85	28.6

样品	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	介孔体积 /cm³·g^-1	平均孔径/nm
USY-14	472	0.587	0.270	5.1
USY-19	523	0.622	0.309	5.7
USY-23	537	0.635	0.321	6.1
USY-29	589	0.668	0.364	6.3

样品	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	介孔体积 /cm³·g^-1	平均孔径/nm
USY-14	472	0.587	0.270	5.1
USY-19	523	0.622	0.309	5.7
USY-23	537	0.635	0.321	6.1
USY-29	589	0.668	0.364	6.3

样品	总酸量 /μmol·g^-1				中强酸量 /μmol·g^-1
样品	B	L	B+L	B/L	B	L	B+L	B/L
USY-14	61.1	20.8	81.9	2.94	47.5	18.8	66.3	2.53
USY-19	46.8	25.7	72.5	1.82	35.4	24.7	60.1	1.43
USY-23	40.3	28.8	69.1	1.40	34.6	21.8	58.4	1.45
USY-29	36.9	30.4	67.3	1.21	32.6	24.7	57.3	1.32

Influence of the SiO₂/Al₂O₃ ratio on the performance of USY zeolites for the gas-phase dehydration of glycerol to acrolein

超稳Y型分子筛的骨架硅铝比对甘油气相脱水反应的影响

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Figures/Tables 9

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反应时间/h	USY-14		USY-19		USY-23		USY-29
反应时间/h	X/%	Y _acro /%	X/%	Y _acro/%	X/%	Y _acro/%	X/%	Y _acro/%
1	46.3	28.3	57.9	35.5	68.0	41.7	84.5	51.8
2	26.9	16.2	31.5	18.1	45.5	27.7	68.3	41.2
3	23.6	13.7	30.2	16.0	41.7	23.0	55.3	31.2
4	16.0	8.9	25.7	9.9	27.2	10.9	46.5	18.4

催化剂	产物分布 /%
催化剂	丙烯醛	丙烯酸	丙烯醇	丙酮	丙酮醇	小分子醛类
USY-14	28.3	1.65	0.37	0.60	2.80	2.83
USY-19	35.5	2.18	0.70	1.39	4.26	3.30
USY-23	41.7	2.45	1.41	1.73	6.72	3.66
USY-29	51.8	2.65	2.13	2.56	8.02	5.52

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