Cs/SiO2-ZrO2催化丙酸甲酯与甲醛缩合反应性能研究

doi:10.19964/j.issn.1006-4990.2024-0114

Abstract

Abstract:

The preparation of Methyl Methacrylate（MMA） by condensation of methyl propionate with formaldehyde hydroxyl aldehyde is currently the cleanest process route，and the key lies in the development of high-performance catalysts.A series of SiO₂-ZrO₂ composite oxides were prepared by coprecipitation and employed as carrier to load Cs₂CO₃ with an incipient wetness impregnation method.The physiochemical properties of the obtained SiO₂-ZrO₂ composite oxides and Cs/SiO₂-ZrO₂ catalysts were characterized by multiple techniques including XRD，Raman，ICP-OES，BET，NH₃-TPD and CO₂-TPD，and correlated to their performances in the condensation reaction of methyl propionate with formaldehyde.Special attention had been paid to the influence of carrier surface acidity and alkalinity on the activity of Cs/SiO₂-ZrO₂ catalysts towards the condensation reaction.The results indicated a transformation of zirconia from m-ZrO₂ to t-ZrO₂ with increasing the SiO₂ content，suggesting t-ZrO₂ was more stable in the SiO₂-ZrO₂ composites with higher SiO₂ contents.Introduction of Cs₂CO₃ onto SiO₂-ZrO₂ composites changed greatly the distribution of surface acid-base sites，as well as the catalyst structure.The weakly basic sites on the catalyst surface were suitable active centers，and there existed an optimal interval between the number of weakly basic and total basic sites on the surface of catalysts with high catalytic activity，in which the reduction of medium-strongly basic sites and the elimination of acidic sites were favourable to the increase of catalytic activity.The 10Cs/60SiO₂-40ZrO₂ catalyst with 60% SiO₂ and 10% Cs₂CO₃ exhibited the best catalytic performances，yielding the conversion of methyl propionate and the selectivity of methyl methacrylate（MMA） up to 30.77% and 97.89%，respectively，under the optimal reaction conditions of 370 ℃，0.2 MPa，and a space velocity of 1.0 h^-1.

Key words: methyl methacrylate, aldol condensation, composite oxides, SiO₂-ZrO₂, methyl propionate

CLC Number:

TQ426.6

DU Haigang, WANG Xingyong, SUN Peiyong, CHEN He, FU Songbao, YAO Zhilong. Study on condensation performance between methyl propionate and formaldehyde catalyzed by Cs/SiO₂-ZrO₂[J]. Inorganic Chemicals Industry, 2024, 56(11): 165-174.

Figures/Tables 17

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SiO₂-ZrO₂ 复合氧化物	比表面积/ （m²·g^-1）	平均孔径/ nm	孔体积/ （10^-1 cm³·g^-1）
30SiO₂-70ZrO₂	117.9	3.8	1.5
40SiO₂-60ZrO₂	136.6	4.2	1.9
50SiO₂-50ZrO₂	152.2	4.8	2.5
60SiO₂-40ZrO₂	164.9	5.4	3.2
70SiO₂-30ZrO₂	173.6	4.8	3.8

SiO₂-ZrO₂ 复合氧化物	碱性位点数量/（mmol·g^-1）				酸性位点数量/（mmol·g^-1）
SiO₂-ZrO₂ 复合氧化物	弱碱	中强碱	强碱	总碱	弱酸	中强酸	强酸	总酸
30SiO₂-70ZrO₂	1.54	0.34	0.06	1.94	0.11	0.28	0.02	0.41
40SiO₂-60ZrO₂	1.16	0.30	0.02	1.48	0.11	0.27	0.03	0.41
50SiO₂-50ZrO₂	1.00	0.19	0.04	1.23	0.11	0.27	0.02	0.40
60SiO₂-40ZrO₂	0.72	0.23	0.05	1.00	0.08	0.11	0.01	0.20
70SiO₂-30ZrO₂	0.53	0.37	0.01	0.91	0.10	0.18	0.01	0.29

催化剂	比表面积/ （m²·g^-1）	平均孔径/ nm	孔体积/ （10^-1 cm³·g^-1）
10Cs/30SiO₂-70ZrO₂	59.0	3.8	1.0
10Cs/40SiO₂-60ZrO₂	68.0	4.5	1.3
10Cs/50SiO₂-50ZrO₂	74.9	4.6	1.7
10Cs/60SiO₂-40ZrO₂	73.6	5.7	2.2
10Cs/70SiO₂-30ZrO₂	71.9	5.7	2.7
6Cs/60SiO₂-40ZrO₂	107.0	5.4	2.5
8Cs/60SiO₂-40ZrO₂	84.2	5.7	2.3
10Cs/60SiO₂-40ZrO₂	73.6	5.7	2.2
12Cs/60SiO₂-40ZrO₂	61.5	7.5	1.9

催化剂	碱性位点数量/（mmol·g^-1）				酸性位点数量/（mmol·g^-1）
催化剂	弱碱	中强碱	强碱	总碱	弱酸	中强酸	强酸	总酸
10Cs/30SiO₂-70ZrO₂	0.43	0.08	—	0.51	0.01	0.01	—	0.02
10Cs/40SiO₂-60ZrO₂	0.69	0.12	—	0.81	0.01	0.01	—	0.02
10Cs/50SiO₂-50ZrO₂	0.64	0.12	—	0.76	—	0.01	—	0.01
10Cs/60SiO₂-40ZrO₂	0.62	0.10	—	0.72	—	—	—	—
10Cs/70SiO₂-30ZrO₂	0.77	0.05	—	0.82	—	—	—	—
6Cs/60SiO₂-40ZrO₂	0.52	0.11	—	0.63	0.01	0.01	—	0.02
8Cs/60SiO₂-40ZrO₂	0.58	0.08	—	0.66	—	0.01	—	0.01
10Cs/60SiO₂-40ZrO₂	0.62	0.10	—	0.72	—	—	—	—
12Cs/60SiO₂-40ZrO₂	0.65	0.08	—	0.73	—	—	—	—

催化剂	X_MP/%	S_MMA/%	S_MIB/%	S_MAL/%	S_C8/%	S_DME/%
30SiO₂-70ZrO₂	9.27	61.62	16.88	1.14	—	20.36
10Cs/30SiO₂-70ZrO₂	27.59	95.42	2.17	1.34	1.07	—
10Cs/40SiO₂-60ZrO₂	29.29	96.12	1.98	1.17	0.73	—
10Cs/50SiO₂-50ZrO₂	30.34	97.66	1.88	0.19	0.27	—
10Cs/60SiO₂-40ZrO₂	30.77	97.89	2.11	—	—	—
10Cs/70SiO₂-30ZrO₂	29.68	96.86	1.43	1.71%	—	—
6Cs/60SiO₂-40ZrO₂	21.90	97.77	0.97	0.76	0.50	—
8Cs/60SiO₂-40ZrO₂	23.50	97.64	1.87	0.19	0.30	—
10Cs/60SiO₂-40ZrO₂	30.77	97.89	2.11	—	—	—
12Cs/60SiO₂-40ZrO₂	20.43	97.97	2.03	—	—	—

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on condensation performance between methyl propionate and formaldehyde catalyzed by Cs/SiO₂-ZrO₂

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