SiO2网络限域CuO纳米晶的甲醛乙炔化性能研究

doi:10.11949/0438-1157.20210239

摘要/Abstract

摘要：

甲醛与乙炔缩合制取1,4-丁炔二醇是乙炔化工的重要方向。探讨铜基催化剂在甲醛乙炔化反应中的演变及催化作用机制，并开发更高效的甲醛乙炔化催化剂是一个值得科学与产业界关注的课题。本工作在前期页硅酸铜催化剂制备及甲醛乙炔化性能研究基础上，进一步通过热处理温度的调整，在焙烧温度为650℃时，构筑了限域于SiO₂网络结构中的CuO纳米晶催化剂。CuO纳米晶适宜的化学环境，使其在甲醛乙炔化反应初始阶段快速形成活性炔化亚铜，获得了1,4-丁炔二醇收率80%左右的结果，克服了页硅酸铜物种转化为炔化亚铜速率慢、诱导期长的弊端。SiO₂网络结构的限域作用也进一步抑制了活性组分的流失，在6次套用实验中1,4-丁炔二醇收率几乎不变，呈现出良好的使用稳定性。

关键词: 催化, 焙烧, 限域, 页硅酸铜, 制备, 稳定性, 甲醛乙炔化, 1,4-丁炔二醇

Abstract:

The synthesis of 1,4-butynediol by the condensation of formaldehyde and ethynyl is an important reaction in ethynyl chemical industry. The study on catalytic mechanism and evolution of Cu-based catalysts in the acetylene reaction of formaldehyde has attracted more and more attention. In this work, on the basis of the preparation of copper silicate catalyst and the performance of formaldehyde ethynylation in the previous stage, and further through the adjustment of the heat treatment temperature, when the calcination temperature is 650℃, a CuO nanocrystalline catalyst confined in the SiO₂ network structure was constructed. Due to suitable chemical environment of CuO nanocrystals, cuprous ethynylation is formed rapidly in the initial stage of the formaldehyde ethynylation reaction, and the yield of about 80% of 1,4-butynediol is obtained. The initial activity is higher than that of the same kinds of catalyst. More importantly, the catalyst showed good stability due to the confined effect of the SiO₂ network structure. The yield of 1,4-butynediol was almost unchanged in 6 application experiments, showing good stability.

Key words: catalysis, calcination, confinement, copper phyllosilicate, preparation, stability, formaldehyde ethynylation, 1,4-butynediol

中图分类号:

TQ 028.8

李海涛, 孟平凡, 张因, 武瑞芳, 黄鑫, 班丽君, 韩旭东, 席琳, 王兴皓, 田博辉, 赵永祥. SiO₂网络限域CuO纳米晶的甲醛乙炔化性能研究[J]. 化工学报, 2021, 72(9): 4708-4717.

Haitao LI, Pingfan MENG, Yin ZHANG, Ruifang WU, Xin HUANG, Lijun BAN, Xudong HAN, Lin XI, Xinghao WANG, Bohui TIAN, Yongxiang ZHAO. Study on formaldehyde ethynylation performance of CuO nanocrystalline confined in SiO₂ networks[J]. CIESC Journal, 2021, 72(9): 4708-4717.

图/表 13

图1 CuO-SiO2前体的TG/DTG-MS曲线

Fig.1 TG/DTG-MS curves of CuO-SiO2 precursors

图2 不同温度处理的CuO-SiO2催化剂的N2吸、脱附等温线与孔径分布曲线

Fig.2 N2 adsorption/desorption isotherm and pore size distribution curves of CuO-SiO2 catalyst treated with different temperatures

表1 催化剂的织构性能和CuO晶粒尺寸

Table 1 Textural properties and CuO crystalline size of catalysts

Catalyst	比表面积A_BET /(m² ·g^-1)^①	孔径D_pore/nm^①	孔体积V_Total/(cm³·g^-1)^①	Cuo晶粒尺寸D_CuO/nm^②
CuO-SiO₂	549	5.05	0.69	—
CuO-SiO₂-350	532	4.75	0.63	—
CuO-SiO₂-450	502	4.94	0.62	—
CuO-SiO₂-550	499	4.89	0.61	—
CuO-SiO₂-650	392	5.43	0.51	5.6
CuO-SiO₂-750	312	5.63	0.45	8.6
CuO-SiO₂-850	150	7.36	0.28	11.4

图3 不同温度处理CuO-SiO2的XRD谱图

Fig.3 XRD patterns of CuO-SiO2 treated at different temperatures

图4 不同温度处理CuO-SiO2的TEM图

Fig.4 TEM images of CuO-SiO2 treated with different temperatures

图5 不同温度处理CuO-SiO2的红外光谱

Fig.5 FT-IR spectra of CuO-SiO2 treated with different temperatures

图6 不同温度下CuO-SiO2的拉曼光谱

Fig.6 Raman spectra of CuO-SiO2 treated with different temperatures

图7 不同温度处理CuO-SiO2的XPS谱图

Fig.7 XPS spectra of CuO-SiO2 treated with different temperatures

表2 CuO-SiO2中Cu形态的化学环境

Table 2 Chemical environment of Cu species in CuO-SiO2

Catalyst	Before reaction				After reaction
	Peak binding energy/eV		Cu²⁺(Ⅰ)/Cu²⁺(Ⅱ)	Cu/Si	Peak kinetic energy/eV		Cu⁺/Cu²⁺
	Cu²⁺(Ⅰ)	Cu²⁺(Ⅱ)	Cu²⁺(Ⅰ)/Cu²⁺(Ⅱ)	Cu/Si	Cu⁺	Cu²⁺	Cu⁺/Cu²⁺
CuO-SiO₂-450	934.1	936.3	0.05	0.54	915.0	917.3	1.71
CuO-SiO₂-650	934.4	936.6	0.17	0.36	915.1	917.7	4.82
CuO-SiO₂-850	934.7	936.8	2.08	0.13	915.0	917.5	3.48

图8 CuO-SiO2 不同焙烧温度下的结构

Fig.8 Structure of CuO-SiO2 at different roasting temperatures

图9 活化CuO-SiO2后的Cu XAES

Fig.9 Cu XAES of CuO-SiO2 after activation

图10 催化剂循环实验图（实验条件:温度90℃;反应时间10 h; C2H2流量30 ml/min）

Fig.10 Cyclic test of catalysts

表3 铜在不同催化剂中的浸出量

Table 3 Leaching content of Cu in different catalysts

Catalyst	Cu in mother liquid/(mg/L)
Catalyst	1 Cycle	3 Cycles	6 Cycles
CuO-SiO₂-450	33.8	35.2	36.5
CuO-SiO₂-650	35.7	37.3	36.2
CuO-SiO₂-850	37.9	39.5	38.4

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SiO₂网络限域CuO纳米晶的甲醛乙炔化性能研究

Study on formaldehyde ethynylation performance of CuO nanocrystalline confined in SiO₂ networks

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