ZrO2/SiO2催化剂的制备及其氧化脱硫性能研究

doi:10.11949/0438-1157.20210457

摘要/Abstract

摘要：

以己内酰胺-八水氧氯化锆低共熔溶剂为添加组分，采用溶胶-凝胶法合成含锆的硅胶，再经过高温煅烧得到n-ZrO₂/SiO₂（n=2%，4%，6%）负载型催化剂。并用红外光谱（FT-IR）、X射线衍射（XRD）、扫描电镜（SEM）、N₂吸附-脱附、X射线光电子能谱（XPS）对其进行结构表征，确定ZrO₂成功负载到SiO₂上。以ZrO₂/SiO₂为催化剂和吸附剂，H₂O₂为氧化剂组成催化氧化脱硫体系，并应用于模拟油脱硫。分别考察了氧化锆负载量、反应温度、氧硫比、催化剂加入量及不同类型的硫化物对脱硫效果的影响。实验结果表明，在反应温度为70℃、n（H₂O₂）/n（S）=4（摩尔比）、4%-ZrO₂/SiO₂的加入量为0.2 g的最佳反应条件下，氧化脱硫体系对二苯并噻吩（DBT）、4，6-二甲基二苯并噻吩（4，6-DMDBT）和苯并噻吩（BT）的脱除率分别为98.7%、93%和65.9%。且4%-ZrO₂/SiO₂回收利用5次后，DBT脱除率仍可达到91.8%。

关键词: ZrO₂/SiO₂, 二苯并噻吩, 溶胶, 氧化, 脱硫

Abstract:

With caprolactam-zirconium oxychloride octahydrate deep eutectic solvent as an additive component, a sol-gel method is used to synthesize zirconium-containing silica-gel, and then through a high-temperature calcination process to obtain n-ZrO₂/SiO₂ (n=2%, 4%, 6%) catalyst. The catalyst were characterized through Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), N₂ adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results show that ZrO₂ was successfully loaded onto SiO₂. The desulfurization of a model oil was investigated using ZrO₂/SiO₂ as the catalyst and adsorbent, H₂O₂ as the oxidant. The effects of ZrO₂ loading, reaction temperature, the molar ratio of O/S, catalyst dosage, and different types of sulfides on the desulfurization were investigated respectively. The experimental results show that under the optimal reaction conditions of 4%-ZrO₂/SiO₂, 70℃ reaction temperature, n(H₂O₂)/n(S)=4, 4%-ZrO₂/SiO₂ dosage of 0.2 g, the sulfur removal rates of DBT, 4,6-DMDBT and BT were 98.7%, 93% and 65.9%. After 4%-ZrO₂/SiO₂ was recycled for 5 times, the desulfurization rate of DBT reached 91.8%.

Key words: ZrO₂/SiO₂, dibenzothiophene, gels, oxidation, desulfurization

中图分类号:

TE 624

刘晓艺, 李秀萍, 赵荣祥, 张豪. ZrO₂/SiO₂催化剂的制备及其氧化脱硫性能研究[J]. 化工学报, 2021, 72(11): 5653-5663.

Xiaoyi LIU, Xiuping LI, Rongxiang ZHAO, Hao ZHANG. Preparation of ZrO₂/SiO₂ catalyst and its oxidative desulfurization performance[J]. CIESC Journal, 2021, 72(11): 5653-5663.

图/表 17

图1 ZrO2/SiO2催化剂的合成过程

Fig.1 The synthesis process of ZrO2/SiO2 catalyst

图2 ZrO2、SiO2、2%-ZrO2/SiO2、4%-ZrO2/SiO2和6%-ZrO2/SiO2的FT-IR谱图

Fig.2 FT-IR spectra of ZrO2, SiO2, 2%-ZrO2/SiO2, 4%-ZrO2/SiO2 and 6%-ZrO2/SiO2

图3 SiO2、2%-ZrO2/SiO2、4%-ZrO2/SiO2和6%-ZrO2/SiO2的XRD谱图

Fig.3 XRD patterns of SiO2, 2%-ZrO2/SiO2, 4%-ZrO2/SiO2 and 6%-ZrO2/SiO2

图4 SiO2和4%-ZrO2/SiO2的SEM照片

Fig.4 SEM images of SiO2 and 4%-ZrO2/SiO2

图5 SiO2、2%-ZrO2/SiO2、4%-ZrO2/SiO2和6%-ZrO2/SiO2的N2吸附-脱附曲线和孔径分布

Fig.5 N2 adsorption-desorption isotherms and pore-size distribution curves of SiO2, 2%-ZrO2/SiO2, 4%-ZrO2/SiO2 and 6%-ZrO2/SiO2

表1 样品的比表面积及孔结构参数

Table 1 Specific surface area and pore structure of samples

Sample

S_BET/(m²/g)

Pore volume/

(cm³/g)

SiO₂

2%-ZrO₂/SiO₂

4%-ZrO₂/SiO₂

526

631

0.4231

0.4602

3.214

2.914

6%-ZrO₂/SiO₂

510

0.3971

3.112

图6 4%-ZrO2/SiO2的XPS谱图

Fig.6 XPS spectrum of 4%-ZrO2/SiO2

图7 氧化锆负载量对脱硫率的影响

Fig.7 Influence of zirconia loading on desulfurization rate(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=6, T=70℃, m4%-ZrO2/SiO2=0.2 g)

图8 温度对脱硫率的影响

Fig.8 Influence of temperature on desulfurization rate(reaction conditions: V(model oil) =5 ml, n(H2O2)/n(S)=6,m4%-ZrO2/SiO2=0.2 g)

图9 4%-ZrO2/SiO2 的加入量对脱硫率的影响

Fig.9 Influence of 4%-ZrO2/SiO2 amount on desulfurization rate(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=6, T=70℃)

图10 氧硫比对脱硫率的影响

Fig.10 Influence of n(H2O2)/n(S) molar rate on desulfurization rate(reaction conditions: V (model oil) =5 ml, T=70℃, m4%-ZrO2/SiO2=0.2 g)

图11 不同硫化物的脱除效果(reaction conditions: (a) V (model oil) =5 ml, T=70℃, m4%-ZrO2/SiO2=0.2 g, t=180 min; (b) V (model oil) =5 ml, T=70℃, m4%-ZrO2/SiO2=0.2 g, n(H2O2)/n(S)=4)

Fig.11 Removal efficiency of different sulfides

图12 氧化脱硫反应中不同硫化物脱除的动力学分析(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=4, T=70℃, m4%-ZrO2/SiO2=0.2 g)

Fig.12 Kinetic analysis of removal of different sulfides in oxidative desulphurization

图13 ZrO2/SiO2催化剂循环使用性能(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=4, T=70℃, m4%-ZrO2/SiO2=0.2 g)

Fig.13 ZrO2/SiO2 recycling performance of catalyst

图14 新鲜催化剂与回收催化剂的红外谱图

Fig.14 Infrared spectra of fresh and recovered catalysts(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=4, T=70℃, m4%-ZrO2/SiO2=0.2 g)

图15 自由基捕捉实验

Fig.15 Free radical capture experiment(reaction conditions: V (model oil) =5 ml, n(H2O2)/n(S)=4, T=70℃, m4%-ZrO2/SiO2=0.2 g)

图16 ZrO2/SiO2脱硫机理

Fig.16 Desulfurization mechanism of ZrO2/SiO2

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ZrO₂/SiO₂催化剂的制备及其氧化脱硫性能研究

Preparation of ZrO₂/SiO₂ catalyst and its oxidative desulfurization performance

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