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第 35 卷第 9 期 精 细 化 工 Vol.35, No.9
201 8 年 9 月 FINE CHEMICALS Sept. 2018

催化与分离提纯技术
NHPI/SMA-Co 催化氧气氧化环己烷的工艺研究

*
许庆博，陈 梦，时 爽，徐思思，周宝晗，唐 强，徐保明
（湖北工业大学 材料与化学工程学院，湖北 武汉 430068）

摘要：以聚苯乙烯马来酸酐共聚物（SMA）及六水合硝酸钴为原料，制备了苯乙烯-马来酸酐钴盐(SMA-Co)，
利用 FTIR、元素分析、UV-vis、SEM、EDS、XRD、TG 对催化剂结构与性能进行了表征与测试。将 N-羟基邻
苯二甲酰亚胺（NHPI）与 SMA-Co 组成复合催化体系，考察了 NHPI 与 SMA-Co 物质的量比、催化剂用量、
反应温度、氧气压力、反应时间对 NHPI/SMA-Co 催化氧气氧化环己烷反应的影响。结果表明：当环己烷
为 5 mL、乙腈为 10 mL、n(NHPI) : n(SMA-Co)=10 : 3、NHPI/SMA-Co 用量 0.04 g、反应温度 120 ¥，初始氧
气压力为 1.0 MPa、反应 6 h 时，环己烷转化率最大，为 19.84%，环己醇选择性为 22.23%，环己酮选择性为 38.65%，
环己酮和环己醇（KA 油）总选择性达 60.88%。催化剂经过 4 次回收利用后，催化剂活性无明显降低。
关键词：SMA-Co；NHPI；环己烷；催化氧化；催化技术
中图分类号：TQ314 文献标识码：A 文章编号：1003-5214 (2018) 09-1567-07

Study on Oxidation of Cyclohexane Catalyzed by Oxygen over

NHPI/SMA-Co

XU Qing-bo, CHEN Meng, SHI Shuang, XU Si-si, ZHOU Bao-han,
*
TANG Qiang, XU Bao-ming
（Hubei University of Technology, School of Materials and Chemical Engineering, Wuhan 430068, Hubei, China）

Abstract: Styrene-maleic anhydride copolymer cobalt salt (SMA-Co) was prepared using styrene-maleic
anhydride copolymer (SMA) and cobalt nitrate hexahydrate as raw materials. The sample was characterized
by FTIR, elemental analysis, UV-vis, SEM, EDS, XRD and TG. Subsequently, a composite catalytic system
composed of N-hydroxyphthalmide (NHPI) and SMA-Co for the oxidation of cyclohexane was constructed.
The effects of molar ratio of NHPI to SMA-Co, catalyst dosage, reaction temperature, oxygen pressure,
reaction time on the oxidation of cyclohexane were investigated. The optimized reaction conditions were
obtained as follows: 5 mL cyclohexane, 10 mL acetonitrile, n(NHPI) : n(SMA-Co)=10 : 3,NHPI/SMA-Co
dosage 0.04 g, reaction temperature 120 ¥, initial oxygen pressure 1.0 MPa, reaction time 6 h. Under these
conditions, the conversion of cyclohexane was 19.84%, and the selectivities of cyclohexanol and
cyclohexanone were 22.23% and 38.65%, respectively. The selectivity of KA oil (the mixture of
cyclohexanone and cyclohexanol) was 60.88%. The catalytic activity of the catalyst was not obviously
reduced after being recycled four times, indicating that the catalyst could be recycled.
Key words: SMA-Co; NHPI; cyclohexane; catalytic oxidation; catalysis technology
Foundation items: National Natural Science Foundation of China (21272086); Ministry of Science and
Technology Small and Medium-sized Enterprise Venture Funds (12C26214204453)

环己酮和环己醇（统称 KA 油）是制造己内酰 很多学者研究了环己烷氧化合成 KA 油和己二酸的
[6]
胺（合成尼龙-6 的单体）的原料，而其进一步的氧 反应 [4-5] 。分子氧作为氧化反应中最为理想的氧源 ，
化产物己二酸则是合成聚酰胺（尼龙-66）的单体 [1-3] 。 其供氧能力可以达到 100%，同时，其具有来源广

收稿日期：2017-08-10; 定用日期：2018-01-12; DOI: 10.13550/j.jxhg.20170649
基金项目：国家自然科学基金（21272086）; 科技部中小企业创业基金（12C26214204453）
作者简介：许庆博（1992—），男，硕士生。联系人：徐保明（1966—），男，教授，电话：027-59750481，E-mail：xubaoming897@163.com。