摘要
与传统工艺相比,丁二烯氢氰化法制备己内酰胺具有绿色、经济、环境友好等特点,其中,己二腈(ADN)部分加氢制备6-氨基己腈(ACN)是该工艺的核心步骤。以尿素为沉淀剂,以Ca O为载体采用沉积沉淀法制备了Ni/Ca O和Ni-Fe/Ca O催化剂,采用TEM、XRD、N_(2)物理吸附-脱附、XPS、H_(2)-TPR对其进行了表征,并将其应用于ADN部分加氢制备ACN,考察了反应温度、反应压力、反应时间对ADN加氢性能的影响。结果表明,Fe掺杂后的催化剂生成了Fe Ni_(3)合金相;Fe掺杂后使金属Ni更加分散。在80℃、4 MPa、Ni-Fe/Ca O催化剂用量为0.10 g的温和条件下反应2 h,ADN转化率为87.5%,ACN选择性为74.4%,失活后的催化剂经过H_(2)还原后能够重复使用。
Compared with the traditional process,the preparation of caprolactam by butadiene has the characteristics of green,economical and environmentally friendly,in which the partial hydrogenation of adiponitrile(ADN)to produce 6-aminohexonitrile(ACN)is the core step of the process.Ni/CaO and Ni-Fe/CaO catalysts were synthesized via deposition-precipitation method using urea as precipitant and CaO as support,characterized by TEM,XRD,N2 physical adsorption and desorption,XPS and H2-TPR,and then applied to catalyze the partial hydrogenation of ADN to obtain ACN.The effects of reaction temperature,pressure and time on the hydrogenation performance of ADN were investigated.The results showed that FeNi_(3) alloy phase was formed in the catalyst after Fe doping,and Fe doping made metal Ni become more dispersed.ADN conversion rate and ACN selectivity reached 87.5%and 74.4%,respectively,under mild conditions of 80℃,4 MPa,Ni-Fe/CaO catalyst dosage of 0.1 g,and reaction time of 2 h.In addition,the deactivated catalyst could be regenerated after H2 reduction.
作者
蒋春月
张海涛
苏东宁
荣泽明
JIANG Chunyue;ZHANG Haitao;SU Dongning;RONG Zeming(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China;Dalian Changxing Catalytic Technology Co.Ltd.,Dalian 116024,Liaoning,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2023年第12期2689-2695,2704,共8页
Fine Chemicals
基金
国家重点研发计划专项(2019YFC1803804-03)
中央高校基本科研专项资金资助项目(DUT2022TB10)
辽宁省自然科学基金项目(2020-MS-17)。
关键词
己二腈部分加氢
6-氨基己腈
沉积沉淀法
双金属催化剂
选择性加氢
催化技术
partial hydrogenation of adiponitrile
6-aminohexanenitrile
deposition-precipitation method
bimetallic catalysts
selective hydrogenation
catalysis technology
