Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts

PENG Jie; YU Yang; WANG Wei; ZHU Donghong; LI Tingting

doi:10.12434/j.issn.2097-2547.20240334

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Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts

更新时间：2025-04-27

- Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts
- Vol. 50, Issue 4, Pages: 64-70(2025)
- 作者机构：
  
  1.南京大学化学化工学院，江苏南京 210023
  2.中石化南京化工研究院有限公司，江苏南京 210048
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240334
  CLC： TQ234.2;O643.3
- Received：13 August 2024，
  
  Revised：2024-09-04，
  
  Published：25 April 2025
- 稿件说明：
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彭洁,于杨,王伟等.老化时间对铜硅环己醇脱氢催化剂副产物苯酚选择性的影响[J].低碳化学与化工,2025,50(04):64-70.

PENG Jie,YU Yang,WANG Wei,et al.Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):64-70.
彭洁,于杨,王伟等.老化时间对铜硅环己醇脱氢催化剂副产物苯酚选择性的影响[J].低碳化学与化工,2025,50(04):64-70. DOI： 10.12434/j.issn.2097-2547.20240334.

PENG Jie,YU Yang,WANG Wei,et al.Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):64-70. DOI： 10.12434/j.issn.2097-2547.20240334.

摘要

铜硅催化剂在催化环己醇脱氢制环己酮时表现良好，而降低副产物苯酚选择性是工业环己醇脱氢催化剂的研究重点。采用沉淀法制备了不同老化时间的铜硅催化剂（C-1（老化时间0 min）、C-2（老化时间30 min）和C-3（老化时间1 h）），考察了老化时间对催化剂催化性能的影响。采用XRD、TEM、H

-TPR、FT-IR和N

物理吸/脱附等分析了催化剂的物化性质，并考察了其催化性能。选取苯酚选择性最低的催化剂（C-2）进行了工业化生产和应用分析。结果表明，随着老化时间延长，催化剂比表面积和活性组分CuO晶粒度逐渐增大，孔容和平均孔径先增大后减小。老化时间为30 min时，CuO与载体SiO

之间形成较强相互作用。3种催化剂的环己醇转化率均超51.00%，环己酮选择性超98.00%。其中，C-2的苯酚选择性最低（0.70%），且该催化剂在水合法环己酮装置中的工业应用结果也证实了其具有良好的抑制苯酚生成的性能。相同制备条件下，调节老化时间可以改变催化剂活性组分的堆积

形态及金属-载体相互作用，进而影响特定副产物选择性。

Abstract

Copper-silicon catalysts exhibit excellent performance in the dehydrogenation of cyclohexanol to cyclohexanone

and reducing the selectivity of by-product phenol is a key research focus of industrial catalysts for cyclohexanol dehydrogenation. Copper-silicon catalysts with different aging time (C-1 (aging time of 0 min)

C-2 (aging time of 30 min) and C-3 (aging time of 1 h)) were prepared by precipitation method

and the effect of aging time on the catalytic performance of the catalysts was investigated. The physical and chemical properties of the catalysts were analyzed by XRD

TEM

-TPR

FT-IR and N

physical adsorption/desorption

and their catalytic performances were investigated. The catalyst (C-2) with the lowest phenol selectivity was selected for industrial production and application analysis. The results show that with extension of aging time

the specific surface area and crystallite size of the active component CuO gradually increase

while the pore volume and average pore size initially increase and then decrease. When the aging time is 30 min

strong interaction between CuO and the support SiO

is formed. In the dehydrogenation of cyclohexanol to cyclohexanone

the conversion of cyclohexanol is over 51.00% and the selectivity of cyclohexanone is over 98.00%. Among them

C-2 exhibits the lowest phenol selectivity (0.7%)

and its industrial application in a cyclohexene hydration method for cyclohexanone production plant further confirms its excellent ability to suppress phenol formation. Under the same preparation conditions

adjusting the aging time can modify the accumulation morphology of the active components and metal-support interactions

thereby influencing the selectivity of specific by-products.

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references

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