H3PW12O40/酸改性硅藻土催化剂的制备、表征及催化合成乙酸正丁酯

doi:10.16085/j.issn.1000-6613.2019-0813

摘要/Abstract

摘要：

以硫酸改性后的硅藻土为载体，Keggin结构磷钨酸为活性组分，通过浸渍法制备出负载型催化剂H₃PW₁₂O₄₀/改性硅藻土，并对催化剂进行傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、扫描电镜（SEM）、X射线能谱（EDS）和N₂-程序升温脱附（N₂-TPD）表征。结果表明：酸改性后硅藻土的微孔增大增多，比表面积增大。H₃PW₁₂O₄₀均匀分布在改性硅藻土载体上，负载后磷钨酸仍保持Keggin结构。以H₃PW₁₂O₄₀/改性硅藻土为催化剂催化乙酸和正丁醇液相合成乙酸正丁酯，通过正交试验探索优化工艺条件。在较优工艺条件下，即w(40%H₃PW₁₂O₄₀/改性硅藻土)=1.1%（基于反应物质量），n(酸)∶n(醇)=1∶3，125℃反应2.0h，酯化率高达98.1%。催化剂重复催化使用5次，酯化率仍可达86.1%。H₃PW₁₂O₄₀/改性硅藻土可作为催化合成乙酸正丁酯的高效催化剂，具有活性高、用量少、价格低廉、制备简单、后处理简便、无废液排放等优点。

关键词: 酸改性硅藻土, keggin结构磷钨酸, 催化剂, 合成, 乙酸正丁酯, 酯化

Abstract:

The supported catalyst of H₃PW₁₂O₄₀/acid modified diatomite was prepared by using the acid modified diatomite as carrier and Keggin type phosphotungstic acid as active constituents. The catalyst was characterized by FTIR, XRD, SEM, EDS and N₂-TPD. The results showed that acid modification obviously increased the BET specific surface area and the pore structure of diatomite. Phosphotungstic acid kept Keggin type after distributed on the surface or inside the pore of acid modified diatomite. The synthesis of n-butyl acetate from acetic acid with n-butanol using the H₃PW₁₂O₄₀/acid modified diatomite as catalyst was studied. The optimum reaction conditions were optimized via orthogonal tests, which was as follows: the mass percentage of 40% H₃PW₁₂O₄₀/acid modified diatomite of 1.1%, based on the total reactants, the mole ratio of acetic acid to n-butanol of 1∶3, reaction temperature 125℃ and reaction time 2.0h, under which the yield of n-butyl acetate was 98.1%. H₃PW₁₂O₄₀/acid modified diatomite catalyst could be reused for 5 times and the yield of n-butyl acetate was still above 86.1%. The catalyst for the esterification reaction has many advantages such as easy preparation, low cost, high activity, simple post-treatment, non-corrosive to equipment and no pollution.

Key words: acid modified diatomite, H₃PW₁₂O₄₀, catalyst, synthesis, n-butyl acetate, esterification

中图分类号:

TQ426.91

周德志,曹小华,占昌朝,史文静,谢宝华. H₃PW₁₂O₄₀/酸改性硅藻土催化剂的制备、表征及催化合成乙酸正丁酯[J]. 化工进展, 2020, 39(2): 554-560.

Dezhi ZHOU,Xiaohua CAO,Changchao ZHAN,Wenjing SHI,Baohua XIE. Preparation, characterization of acid modified diatomite supported H₃PW₁₂O₄₀ and its catalytic performance for n-butyl acetate synthesis[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 554-560.

图/表 9

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催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔半径/nm
H₃PW₁₂O₄₀·nH₂O	3.75	0.037	8.62
硅藻土	21.31	0.65	58.37
酸改性硅藻土	47.43	0.98	75.21
40% HPW/硅藻土	15.23	0.43	47.69
10%HPW/酸改性硅藻土	36.74	0.67	58.74
20%HPW酸改性硅藻土	35.57	0.63	56.34
30%HPW/酸改性硅藻土	33.85	0.59	55.29
40%HPW/酸改性硅藻土	31.34	0.51	53.21
50%HPW/酸改性硅藻土	19.72	0.46	47.17
60%HPW/酸改性硅藻土	13.32	0.32	36.19
回收40%HPW/酸改性硅藻土	19.56	0.43	46.73

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔半径/nm
H₃PW₁₂O₄₀·nH₂O	3.75	0.037	8.62
硅藻土	21.31	0.65	58.37
酸改性硅藻土	47.43	0.98	75.21
40% HPW/硅藻土	15.23	0.43	47.69
10%HPW/酸改性硅藻土	36.74	0.67	58.74
20%HPW酸改性硅藻土	35.57	0.63	56.34
30%HPW/酸改性硅藻土	33.85	0.59	55.29
40%HPW/酸改性硅藻土	31.34	0.51	53.21
50%HPW/酸改性硅藻土	19.72	0.46	47.17
60%HPW/酸改性硅藻土	13.32	0.32	36.19
回收40%HPW/酸改性硅藻土	19.56	0.43	46.73

实验编号	酸醇摩尔比	催化剂质量/g	反应温度/℃	反应时间/h	酯化率/%
1	1∶1	0.2	115	2	71.2
2	1∶1	0.3	120	2.5	82.3
3	1∶1	0.4	125	3.0	70.0
4	1∶2	0.2	120	3.0	73.7
5	1∶2	0.3	125	2.0	97.7
6	1∶2	0.4	115	2.5	90.2
7	1∶3	0.2	125	2.5	85.9
8	1∶3	0.3	115	3.0	92.2
9	1∶3	0.4	120	2.0	92.8
K_1/3	74.50	76.94	84.56	87.06
K_2/3	87.20	90.74	82.92	86.13
K_3/3	90.31	84.35	86.66	78.66
R	15.81	13.8	3.74	8.4
最优水平	1∶3	0.3	125	2.0

实验编号	酸醇摩尔比	催化剂质量/g	反应温度/℃	反应时间/h	酯化率/%
1	1∶1	0.2	115	2	71.2
2	1∶1	0.3	120	2.5	82.3
3	1∶1	0.4	125	3.0	70.0
4	1∶2	0.2	120	3.0	73.7
5	1∶2	0.3	125	2.0	97.7
6	1∶2	0.4	115	2.5	90.2
7	1∶3	0.2	125	2.5	85.9
8	1∶3	0.3	115	3.0	92.2
9	1∶3	0.4	120	2.0	92.8
K_1/3	74.50	76.94	84.56	87.06
K_2/3	87.20	90.74	82.92	86.13
K_3/3	90.31	84.35	86.66	78.66
R	15.81	13.8	3.74	8.4
最优水平	1∶3	0.3	125	2.0

催化剂种类	酯化率/%
硅藻土	27.1
酸改性硅藻土	27.6
H₃PW₁₂O₄₀·nH₂O	97.8
40%HPW/未改性硅藻土	93.2
40%HPW/酸改性硅藻土	98.1
98% H₂SO₄	96.4

H₃PW₁₂O₄₀/酸改性硅藻土催化剂的制备、表征及催化合成乙酸正丁酯

Preparation, characterization of acid modified diatomite supported H₃PW₁₂O₄₀ and its catalytic performance for n-butyl acetate synthesis

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