不同pH铝溶胶对二甲醚羰基化成型丝光沸石催化剂性能的影响

doi:10.11949/0438-1157.20240181

摘要/Abstract

摘要：

由合成气生产二甲醚（DME），然后DME羰基化生产乙酸甲酯（MA），MA加氢生成乙醇是一条转化率和选择性高、反应条件温和、分离能耗低的绿色工艺路线。其中二甲醚羰基化反应作为重要的中间反应已经受到了广大学者的高度关注。本文主要针对DME羰基化制MA反应，使用具有高活性和高稳定性的丝光沸石（MOR）制备成型催化剂，为进一步工业化奠定基础。通过使用不同pH的铝溶胶作黏结剂制备一系列丝光沸石成型催化剂，并与使用拟薄水铝石作黏结剂的成型催化剂进行比较。通过强度测试以及Weibull函数统计分析，探究了黏结剂对成型MOR的强度以及强度可靠性的影响；X射线衍射、N₂物理吸附、²⁹Si MAS NMR、吡啶吸附原位红外等表征结合活性评价，探究了黏结剂对MOR的物理结构、酸性以及催化性能的作用。结果表明，铝溶胶的pH对丝光沸石成型催化剂的孔道结构、力学性能和催化性能都有十分重要的影响。铝溶胶的pH在4.9时，成型催化剂介孔比表面积和体积最大（70 m²/g和0.20 cm³/g），机械强度最高（110.7 N/cm），单位分子筛上Brønsted酸量下降幅度最小。因此，单位分子筛上DME转化率和时空收率最高。

关键词: 合成气, 分子筛, 催化剂, 黏结剂, 羰基合成

Abstract:

The production of dimethyl ether (DME) from syngas, followed by the carbonylation of DME to produce methyl acetate (MA), and the hydrogenation of MA to ethanol is a green process route with high conversion and selectivity, mild reaction conditions, and low separation energy consumption. Among them, the dimethyl ether carbonylation reaction, as an important intermediate reaction, has attracted great attention from scholars. The present work focuses on the reaction of carbonylation of DME to MA, using mordenite (MOR) with high carbonylation activity and stability to prepare shaped catalysts, which lays a foundation for further industrialization. A series of extruded MOR catalysts were prepared by using aluminum sol with different pH as binder and compared with shaped catalysts using pseudo-boehmite as binder. The effect of the binder on the strength of the shaped catalysts was investigated by strength tests as well as statistical analysis of the Weibull function. The role of the binder on the physical structure, acidity and catalytic performance of the MOR was investigated by characterization such as X-ray diffraction, N₂ physical adsorption, ²⁹Si MAS NMR, and in-situ pyridine adsorption infrared in combination with the evaluation of catalytic properties. The results showed that the pH of the aluminum sol had a very important effect on the pore structure, mechanical properties and catalytic performance of the shaped catalyst. When the pH of the aluminum sol is 4.9, the extruded catalyst had the largest mesoporous specific surface area and volume (70 m²/g and 0.20 cm³/g), the highest mechanical strength (110.7 N/cm) and the smallest decrease in the amount of Brønsted acid by unit mass of zeolite. Therefore, the extruded catalyst had the highest DME conversion and space-time yield by unit mass of zeolite.

Key words: syngas, zeolite, catalyst, binder, carbonylation

中图分类号:

TQ 203.2

王寅, 初鹏飞, 刘虎, 吕静, 黄守莹, 王胜平, 马新宾. 不同pH铝溶胶对二甲醚羰基化成型丝光沸石催化剂性能的影响[J]. 化工学报, 2024, 75(7): 2533-2543.

Yin WANG, Pengfei CHU, Hu LIU, Jing LYU, Shouying HUANG, Shengping WANG, Xinbin MA. Influence of aluminum sol with different pH on performance of shaped mordenite catalyst for dimethyl ether carbonylation[J]. CIESC Journal, 2024, 75(7): 2533-2543.

图/表 20

图1 未成型MOR及成型催化剂的XRD谱图

Fig.1 XRD patterns of the parent and shaped catalysts

图2 未成型MOR与成型催化剂的N2吸/脱附等温线

Fig.2 Nitrogen adsorption-desorption isotherms of the parent and shaped catalysts

表1 未成型MOR与成型催化剂的物理结构性质

Table 1 Textural properties of parent and shaped catalyet

样品	S_BET/ (m²/g)	S_Micropore/ (m²/g)	S_Mesopore/ (m²/g)	V_Totalpore/ (cm³/g)	V_Micropore/ (cm³/g)	V_Mesopore/ (cm³/g)
MOR	561	538	23	0.33	0.21	0.12
MOR-BH	511	435	76	0.36	0.17	0.19
MOR-3.7	507	454	53	0.35	0.17	0.17
MOR-4.1	493	437	56	0.36	0.17	0.18
MOR-4.9	487	418	70	0.36	0.16	0.20
MOR-7.7	451	401	50	0.33	0.17	0.17

图3 未成型MOR与成型催化剂的微孔尺寸分布

Fig.3 Micropore size distributions of the parent and shaped catalysts

图4 未成型MOR与成型催化剂的介孔尺寸分布

Fig.4 Mesopore size distributions of the parent and shaped catalysts

图5 MOR粉末和不同成型催化剂的断面SEM图

Fig.5 SEM images of MOR powder and cross-sections of shaped catalysts

图6 胶溶后拟薄水铝石和铝溶胶的粒度分布

Fig.6 Particle size distribution of pseudoboehmite after peptization and aluminum sol

图7 成型催化剂的压碎强度

Fig.7 The crushing strength of the shaped catalysts

图8 成型催化剂的Weibull分布

Fig.8 The Weibull distribution of the shaped catalysts

表2 成型MOR催化剂的强度数据统计

Table 2 Statistics of strength data for the shaped MOR

样品	F/(N/cm)	m	R²	F_10%/(N/cm)
MOR-BH	128.6±24.4	5.2	0.87	114.4
MOR-3.7	82.1±11.8	4.8	0.94	74.2
MOR-4.1	87.5±14.6	4.8	0.82	77.5
MOR-4.9	110.7±14.8	5.3	0.87	102.9
MOR-7.7	80.8±14.6	4.2	0.87	67.9

图9 不同成型催化剂的剪切应力

Fig.9 Shear stress with different shaped catalysts

图10 不同成型催化剂的黏度

Fig.10 Viscosity with different shaped catalysts

图11 不同成型催化剂的宏观图片

Fig.11 The photos of different shaped catalysts

图12 MOR和不同成型催化剂的29Si MAS NMR图

Fig.12 29Si MAS NMR spectra of the parent and shaped catalysts

表3 29Si MAS NMR测试及分峰结果

Table 3 The de-convolution results of 29Si MAS NMR profiles

样品	Si(0Al)/%	Si(0Al)/%	Si(1Al)/%	Si(2Al)/%	Si/Al^①
MOR	2.2	66.2	28.8	2.8	11.6
MOR-BH	2.5	69.7	25.8	2.0	13.4
MOR-3.7	3.0	68.9	26.1	2.1	13.2
MOR-4.1	3.2	68.6	26.1	2.1	13.2
MOR-4.9	2.8	67.3	26.2	3.8	11.8
MOR-7.7	2.2	67.6	27.3	2.9	12.1

图13 MOR和不同成型催化剂的吡啶红外光谱图

Fig.13 Pyridine adsorption IR spectra of the parent and shaped catalysts

表4 未成型MOR及成型催化剂酸量

Table 4 The amounts of acid for parent and shaped MOR

样品	B_total/ (μmol/g)	B_12-MR/ (μmol/g)	B_8-MR/ (μmol/g)	B_8-MR/ B_12-MR^①	B_8-MR/ B_12-MR^②
MOR	1320	641	678	1.1	1.1
MOR-BH	1156	571	584	1.0	1.1
MOR-3.7	1173	584	588	1.0	1.1
MOR-4.1	1174	585	589	1.0	1.1
MOR-4.9	1297	633	664	1.1	1.1
MOR-7.7	1274	618	666	1.1	1.1

图14 MOR和不同成型催化剂的羟基区红外光谱图

Fig.14 IR spectra in hydroxyl groups region of the parent and shaped catalysts

图15 MOR和不同成型催化剂上的DME转化率和MA选择性（反应条件：温度200℃，总压1.5 MPa，混合气DME/CO摩尔比1/49，空速9000 h-1）

Fig.15 Conversion of DME and selectivity to MA of the parent and shaped catalysts (reaction conditions: 200℃, 1.5 MPa, DME/CO molar ratio 1/49, 9000 h-1)

图16 单位质量MOR上的质量时空收率

Fig.16 Mass space-time yield per unit mass MOR

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