Effects of SiO<sub>2</sub> promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts

LIU Jie; SUN Yuanlong; LI Tingting; YU Yang; LI Zhongyu; GUO Xuefeng

doi:10.12434/j.issn.2097-2547.20240338

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Effects of SiO₂ promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts

- Effects of SiO₂ promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts
- Pages: 1-8(2024)
- 作者机构：
  
  1.南京大学化学化工学院介观化学教育部重点实验室，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.2097-2547.20240338
  CLC： TQ223.1;TQ426.8
- Published Online：19 November 2024，
  
  Received：15 August 2024，
  
  Revised：04 September 2024，
- 稿件说明：
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刘洁,孙远龙,李婷婷等.SiO₂助剂对铜基催化剂上辛烯醛加氢制辛醇反应副产物选择性的影响[J].低碳化学与化工,

LIU Jie,SUN Yuanlong,LI Tingting,et al.Effects of SiO₂ promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts[J].Low-carbon Chemistry and Chemical Engineering,
刘洁,孙远龙,李婷婷等.SiO₂助剂对铜基催化剂上辛烯醛加氢制辛醇反应副产物选择性的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20240338.

LIU Jie,SUN Yuanlong,LI Tingting,et al.Effects of SiO₂ promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts[J].Low-carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20240338.

摘要

辛烯醛气相法加氢是工业领域生产2-乙基己醇（下称“辛醇”）的主要方法，该过程的副产物种类和选择性对辛醇品质和产量有直接影响。为获得具有较高催化活性的催化剂并控制副产物选择性，制备了铜（Cu）基催化剂，并采用SiO

作为助剂对催化剂进行了改性。评价了所得催化剂（N-1、N-2和N

-3）的辛烯醛气相加氢催化性能，并结合XRD、N

吸/脱附、XPS、TEM、NH

-TPD和Py-IR等多种表征方式对催化剂进行了表征。结果表明，催化剂的催化活性与催化剂中CuO分散度和Lewis酸量相关。其中在入口温度为150 ℃、反应压力为0.4 MPa、辛烯醛进料液空速为0.3 h

-1

的条件下，SiO

含量（质量分数，下同）为0的N-1的辛烯醛转化率为99.76%，辛醇选择性为99.50%，加氢产物中部分加氢副产物2-乙基己醛和2-乙基己烯醇含量分别为0.22%和0.04%，重组分含量为1.06%；SiO

能够修饰催化剂表面性质，定向降低重组分产物选择性，SiO

含量为2%的N-2的辛烯醛转化率为99.49%，辛醇选择性为99.40%，2-乙基己醛、2-乙基己烯醇和重组分含量分别为0.28%、0.06%和0.72%。在总计10个月的工业应用验证中，N-2表现出较好的催化性能，其2-乙基己醛、辛醇和重组分含量的均值依次为小于0.01%、97.88%和0.42%。

Abstract

Gas phase hydrogenation of 2-ethyl-2-hexenal is the main method for industrial production of 2-ethylhexanol (hereinafter referred to as “octanol”). The type and selectivity of by-products in the process have direct impacts on the quality and yield of octanol. To achieve a highly active catalyst and control the selectivity of by-products

copper (Cu)-based catalysts were prepared and modified with SiO

as the promoter. The catalytic performances of obtained catalysts (N-1

N-2 and N-3) for gas phase hydrogenation of 2-ethyl-2-hexenal were measured and the structures of the catalysts were analyzed by XRD

adsorption/desorption

XPS

TEM

-TPD

Py-IR

etc. The results show that the hydrogenation activities of the catalysts are related to the dispersions of CuO and the amounts of Lewis acid in the catalysts. Under the reaction conditions of inlet temperature of 150 ℃

pressure of 0.4 MPa and 2-ethyl-2-hexenal liquid space velocity of 0.3 h

-1

2-ethyl-2-hexenal conversion rate of 99.76% and octanol selectivity of 99.50% are achieved for N-1 with SiO

content (mass fraction

the same below) of 0. The contents of partially hydrogenated by-products 2-ethylhexanal and 2-ethylhexenol in reaction products are 0.22% and 0.04%

respectively

and the content of heavy components is 1.06%. Modification of catalyst surface properties with SiO

can regulate the selectivity of heavy component

s. N-2 with SiO

content of 2% exhibits 2-ethyl-2-hexenal conversion rate of 99.49% and octanol selectivity of 99.40%

with the content of 2-ethylhexanal

2-ethylhexenol and heavy components of 0.28%

0.06% and 0.72%

respectively. During a total of ten months of industrial application verification

N-2 demonstrate superior catalytic performance with average contents of 2-ethylhexanal

octanol and heavy components of less than 0.01%

97.88% and 0.42%

respectively.

关键词

辛烯醛加氢铜基催化剂辛醇SiO2副产物选择性

Keywords

2-ethyl-2-hexenal hydrogenationCu-based catalyst2-ethylhexanolSiO2by-products selectivity

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Effects of SiO2 promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts

DOI：10.12434/j.issn.2097-2547.20240338

摘要

Abstract

关键词

Keywords

references

Effects of SiO₂ promoters on by-products selectivity in 2-ethyl-2-hexenal hydrogenation to 2-ethylhexanol over Cu-based catalysts