V2O5/ZrO2-Al2O3催化甲醇选择性氧化合成二甲氧基甲烷

张丹; 尚润梅; 赵振涛; 李君华; 邢锦娟

doi:10.6054/j.jscnun.2022044

V₂O₅/ZrO₂-Al₂O₃催化甲醇选择性氧化合成二甲氧基甲烷

doi: 10.6054/j.jscnun.2022044

张丹^{1, 2},
尚润梅¹,
赵振涛¹,
李君华^{1, 2, ,},
邢锦娟¹

1.
渤海大学化学与材料工程学院，锦州 121013
2.
辽宁石油化工大学石油化工学院，抚顺 113001

基金项目:

国家自然科学基金项目 21606117

辽宁省高等学校创新团队项目 2018-479-14

辽宁省高等学校创新团队项目 LT2015001

详细信息

通讯作者:
李君华，Email: lijunhua0521@163.com

中图分类号: O643.3
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- 文章访问数: 9
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- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2021-10-20
- 网络出版日期: 2022-07-29
- 刊出日期: 2022-06-25

The Synthesis of Dimethoxymethane through Selective Oxidation of Methanol with V₂O₅/ZrO₂-Al₂O₃ Catalysts

ZHANG Dan^{1, 2},
SHANG Runmei¹,
ZHAO Zhentao¹,
LI Junhua^{1, 2
, ,},
XING Jinjuan¹

1.
College of Chemistry and Materials Engineering, Bohai University, Jinzhou 121013, China
2.
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China

摘要

摘要: 采用浸渍法制备了V₂O₅质量分数不同的V₂O₅/Al₂O₃催化剂，采用Zr对Al₂O₃载体进行改性并应用于催化甲醇选择性氧化制备二甲氧基甲烷(DMM)的反应中。经X-射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见分光光谱(UV-Vis)、傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、N₂吸附-脱附(BET)、H₂程序升温还原(H₂-TPR)和NH₃程序升温脱附(NH₃-TPD)表征分析，结果表明：与单一Al₂O₃负载的钒基催化剂相比，Zr改性提高了钒氧化物的分散性与稳定性，加强了催化剂中各组分间的相互作用，有效调变了催化剂的酸性和氧化性，进而提高了DMM的选择性。考察了反应条件对甲醇选择性氧化制备DMM的影响，最佳反应温度为175 ℃，经20%V₂O₅/12%ZrO₂-Al₂O₃催化氧化，甲醇转化率为27.9%，DMM选择性为99.9%。
- 甲醇选择性氧化 /
- 双功能催化剂 /
- 氧化钒 /
- 二甲氧基甲烷 /
- 改性
Abstract: V₂O₅/Al₂O₃ catalysts with different V₂O₅ mass fraction were prepared with the impregnation method. The support of V₂O₅/Al₂O₃ catalyst was modified with Zr. The catalysts were applied to the selective oxidation of methanol to prepare dimethoxymethane(DMM). The as-prepared catalysts were characterized with X-ray diffraction(XRD), scanning electron microscope (SEM), ultraviolet and visible spectrophotometry (UV-Vis), fourier transform infrared (FTIR), raman spectra (Raman), N₂ adsorption-desorption isotherm (BET), H₂ temperature-programmed reduction(H₂-TPR) and NH₃ temperature-programmed desorption (NH₃-TPD). The results indicated that the performance of Zr modification could effectively improve the dispersibility and stability of vanadium oxide and the interaction between the substances in the catalyst. In addition, compared with vanadium-based catalysts supported on the single oxide Al₂O₃, the Zr modification could effectively regulate the acidity and oxidation properties of the catalyst, which improved the selectivity of DMM. The effect of reaction conditions on the preparation of DMM through methanol oxidation was investigated. For the catalyst 20%V₂O₅/12%ZrO₂-Al₂O₃, the value of methanol conversion and DMM selectivity were 27.9% and 99.9% at 175 ℃, respectively.
- selective oxidation of methanol /
- bifunctional catalysts /
- vanadium oxide /
- dimethoxymethane /
- modification

HTML全文

图 1 催化剂的制备流程

Figure 1. The process of the catalyst preparation

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图 2 不同催化剂的XRD图谱

Figure 2. The XRD patterns of different catalysts

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图 3 不同催化剂的SEM图和EDS图

Figure 3. The SEM and EDS images of different catalysts

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图 4 20%V₂O₅/yZrO₂-Al₂O₃的UV-Vis谱

Figure 4. The UV-Vis spectra of 20%V₂O₅/yZrO₂-Al₂O₃

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图 5 20%V₂O₅/yZrO₂-Al₂O₃的FTIR谱

Figure 5. The FTIR spectra of 20%V₂O₅/yZrO₂-Al₂O₃

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图 6 20%V₂O₅/yZrO₂-Al₂O₃的Raman谱

Figure 6. The Raman spectra of 20%V₂O₅/yZrO₂-Al₂O₃

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图 7 催化剂的N₂吸附脱附等温线和孔径分布

Figure 7. The nitrogen adsorption isotherms and pore width distribution of the catalysts

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图 8 20%V₂O₅/yZrO₂-Al₂O₃的H₂-TPR和NH₃-TPD曲线

Figure 8. The H₂-TPR and NH₃-TPD curves of 20%V₂O₅/yZrO₂-Al₂O₃

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图 9 不同催化剂上反应时间对甲醇转化率和DMM选择性的影响

注：t=175 ℃；WHSV=2.37 h^-1；V(O₂)/V(N₂)=1/4；p=0.01 MPa。

Figure 9. The effect of reaction time on the methanol oxidation with the catalysts

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图 10 20%V₂O₅/12%ZrO₂-Al₂O₃催化剂上反应温度对甲醇转化率和DMM选择性的影响

Figure 10. The influence of reaction temperature on the methanol oxidation over 20%V₂O₅/12%ZrO₂-Al₂O₃ catalyst

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图 11 20%V₂O₅/12%ZrO₂-Al₂O₃催化剂的循环使用性能

Figure 11. The reusability of the 20%V₂O₅/12%ZrO₂-Al₂O₃ catalyst

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图 12 5次循环使用前后20%V₂O₅/12%ZrO₂-Al₂O₃催化剂的XRD图谱

Figure 12. The XRD patterns before and after 5-cycle-reaction for the 20%V₂O₅/12%ZrO₂-Al₂O₃ catalyst

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表 1 催化剂的比表面积和孔结构数据

Table 1. The specific surface area and porosity data of the catalysts

催化剂	比表面积/(m²·g^-1)	孔容积/(cm³·g^-1)		平均孔径/nm
催化剂	比表面积/(m²·g^-1)	总孔	微孔	平均孔径/nm
20%V₂O₅/Al₂O₃	145	0.21	0.08	3.0
20%V₂O₅/4%ZrO₂-Al₂O₃	133	0.22	0.06	5.1
20%V₂O₅/8%ZrO₂-Al₂O₃	125	0.28	0.03	6.9
20%V₂O₅/12%ZrO₂-Al₂O₃	123	0.32	0.02	7.3
20%V₂O₅/16%ZrO₂-Al₂O₃	119	0.30	0.02	7.2
20%V₂O₅/20%ZrO₂-Al₂O₃	110	0.31	0.02	7.3

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